Golf balls having layers made of silicone elastomers

ABSTRACT

Multi-layered golf balls having at least one layer made of a foamed silicone composition are provided. Multi-layered golf balls having at least one layer made of non-foamed silicone elastomer composition also are provided. For example, three-piece, four-piece, and five-piece golf balls containing different core and cover structures can be made. The foamed silicones have good thermal stability and durability without sacrificing resiliency. The non-foamed silicone elastomers have high elongation, tensile strength, chemical/fluid-resistance, and weatherability properties. These compositions can be used to form any layer, for example, core, intermediate, or cover, in the golf ball.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of, co-assigned U.S. patent applicationSer. No. 15/290,175 filed Oct. 11, 2016, now allowed; which is acontinuation-in-part of, co-assigned U.S. patent application Ser. No.15/181,723 filed Jun. 14, 2016, now U.S. Pat. No. 9,814,939 with anissue date of Nov. 14, 2017; which is a continuation of co-assigned U.S.patent application Ser. No. 14/071,819 filed Nov. 5, 2013, now U.S. Pat.No. 9,375,612 with an issue date of Jun. 28, 2016, the entiredisclosures of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates generally to multi-layered, golf ballshaving layers made of foamed and non-foamed compositions. In oneembodiment, a dual-layered core has a silicone foam inner core (center)and surrounding thermoset or thermoplastic outer core layer. In anotherembodiment, a three-layered core having at least one layer made from anon-foamed silicone elastomer composition is prepared. In yet anotherembodiment, a two-layered cover having at least one layer made from anon-foamed silicone elastomer composition is prepared.

Brief Review of the Related Art

Both professional and amateur golfer use multi-piece, solid golf ballstoday. Basically, a two-piece solid golf ball includes a solid innercore protected by an outer cover. The inner core is made of a natural orsynthetic rubber such as polybutadiene, styrene butadiene, orpolyisoprene. The cover surrounds the inner core and may be made of avariety of materials including ethylene acid copolymer ionomers,polyamides, polyesters, polyurethanes, and polyureas.

In recent years, three-piece, four-piece, and even five-piece balls havebecome more popular. These multi-piece balls have become more popularfor several reasons including new manufacturing technologies, lowermaterial costs, and desirable ball playing performance properties. Manygolf balls used today have multi-layered cores comprising an inner coreand at least one surrounding outer core layer. For example, the innercore may be made of a relatively soft and resilient material, while theouter core may be made of a harder and more rigid material. The“dual-core” sub-assembly is encapsulated by a single or multi-layeredcover to provide a final ball assembly. Different materials can be usedto manufacture the core and cover and impart desirable properties to thefinished ball.

In general, dual-cores comprising an inner core (or center) and asurrounding outer core layer are known in the industry. For example,Sugimoto, U.S. Pat. No. 6,390,935 discloses a three-piece golf ballcomprising a core having a center and outer shell and a cover disposedabout the core. The specific gravity of the outer shell is greater thanthe specific gravity of the center. The center has JIS-C hardness (X) atthe center point and JIS-C hardness (Y) at a surface point satisfyingthe equation: (Y−X)≥8. The core structure (center and outer shell) hasJIS-C hardness (Z) at a surface of 80 or greater. The cover has a ShoreD hardness of less than 60.

Endo, U.S. Pat. No. 6,520,872 discloses a three-piece golf ballcomprising a center, an intermediate layer formed over the center, and acover formed over the intermediate layer. The center is preferably madeof high-cis polybutadiene rubber; and the intermediate and cover layersare preferably made of an ionomer resin such as an ethylene acidcopolymer.

Watanabe, U.S. Pat. No. 7,160,208 discloses a three-piece golf ballcomprising a rubber-based inner core; a rubber-based outer core layer;and a polyurethane elastomer-based cover. The inner core layer has JIS-Chardness of 50 to 85; the outer core layer has JIS-C hardness of 70 to90; and the cover has Shore D hardness of 46 to 55. Also, the inner corehas a specific gravity of more than 1.0, and the core outer layer has aspecific gravity equal to or greater than that of that of the innercore.

The core structure as an engine or spring for the golf ball. Thus, thecomposition and construction of the core is a key factor in determiningthe resiliency and rebounding performance of the ball. In general, therebounding performance of the ball is determined by calculating itsinitial velocity after being struck by the face of the golf club and itsoutgoing velocity after making impact with a hard surface. Moreparticularly, the “Coefficient of Restitution” or “COR” of a golf ballrefers to the ratio of a ball's rebound velocity to its initial incomingvelocity when the ball is fired from an air cannon into a rigid verticalplate. The COR for a golf ball is written as a decimal value betweenzero and one. A golf ball may have different COR values at differentinitial velocities. The United States Golf Association (USGA) setslimits on the initial velocity of the ball so one objective of golf ballmanufacturers is to maximize COR under such conditions. Balls with ahigher rebound velocity have a higher COR value. Such golf balls reboundfaster, retain more total energy when struck with a club, and havelonger flight distance as opposed to balls with low COR values. Theseproperties are particularly important for long distance shots. Forexample, balls having high resiliency and COR values tend to travel afar distance when struck by a driver club from a tee.

The durability, spin rate, and feel of the ball also are importantproperties. In general, the durability of the ball refers to theimpact-resistance of the ball. Balls having low durability appear wornand damaged even when such balls are used only for brief time periods.In some instances, the cover may be cracked or torn. The spin raterefers to the ball's rate of rotation after it is hit by a club. Ballshaving a relatively high spin rate are advantageous for short distanceshots made with irons and wedges. Professional and highly skilledamateur golfers can place a back spin more easily on such balls. Thishelps a player better control the ball and improves shot accuracy andplacement. By placing the right amount of spin on the ball, the playercan get the ball to stop precisely on the green or place a fade on theball during approach shots. On the other hand, recreational players whocannot intentionally control the spin of the ball when hitting it with aclub are less likely to use high spin balls. For such players, the ballcan spin sideways more easily and drift far-off the course, especiallyif it is hooked or sliced. Meanwhile, the “feel” of the ball generallyrefers to the sensation that a player experiences when striking the ballwith the club and it is a difficult property to quantify. Most playersprefer balls having a soft feel, because the player experience a morenatural and comfortable sensation when their club face makes contactwith these balls. Balls having a softer feel are particularly desirablewhen making short shots around the green, because the player senses morewith such balls. The feel of the ball primarily depends upon thehardness and compression of the ball.

Manufacturers of golf balls are constantly looking to differentmaterials for improving the playing performance and other properties ofthe ball. For example, golf balls containing cores made from foamcompositions are generally known in the industry. Puckett and Cadorniga,U.S. Pat. Nos. 4,836,552 and 4,839,116 disclose one-piece, shortdistance golf balls made of a foam composition comprising athermoplastic polymer (ethylene acid copolymer ionomer such as Surlyn®)and filler material (microscopic glass bubbles). The density of thecomposition increases from the center to the surface of the ball. Thus,the ball has relatively dense outer skin and a cellular inner core.According to the '552 and '116 patents, by providing a short distancegolf ball, which will play approximately 50% of the distance of aconventional golf ball, the land requirements for a golf course can bereduced 67% to 50%.

Gentiluomo, U.S. Pat. No. 5,104,126 discloses a three-piece golf ball(FIG. 2) containing a high density center (3) made of steel, surroundedby an outer core (4) of low density resilient syntactic foamcomposition, and encapsulated by an ethylene acid copolymer ionomer(Surlyn®) cover (5). The '126 patent defines the syntactic foam as beinga low density composition consisting of granulated cork or hollowspheres of either phenolic, epoxy, ceramic or glass, dispersed within aresilient elastomer.

Aoyama, U.S. Pat. Nos. 5,688,192 and 5,823,889 disclose a golf ballcontaining a core, wherein the core comprising an inner and outerportion, and a cover made of a material such as balata rubber orethylene acid copolymer ionomer. The core is made by foaming, injectinga compressible material, gasses, blowing agents, or gas-containingmicrospheres into polybutadiene or other core material. According to the'889 patent, polyurethane compositions may be used. The compressiblematerial, for example, gas-containing compressible cells may bedispersed in a limited part of the core so that the portion containingthe compressible material has a specific gravity of greater than 1.00.Alternatively, the compressible material may be dispersed throughout theentire core. In one embodiment, the core comprises an inner and outerportion. In another embodiment, the core comprises inner and outerlayers.

Sullivan and Ladd, U.S. Pat. No. 6,688,991 discloses a golf ballcontaining a low specific gravity core, optional intermediate layer, andhigh specific gravity cover with Shore D hardness in the range of about40 to about 80. The core is preferably made from a highly neutralizedthermoplastic polymer such as ethylene acid copolymer which has beenfoamed.

Nesbitt, U.S. Pat. No. 6,767,294 discloses a golf ball comprising: i) apressurized foamed inner center formed from a thermoset material, athermoplastic material, or combinations thereof, a blowing agent and across-linking agent and, ii) an outer core layer formed from a secondthermoset material, a thermoplastic material, or combinations thereof.Additionally, a barrier resin or film can be applied over the outer corelayer to reduce the diffusion of the internal gas and pressure from thenucleus (center and outer core layer). Preferred polymers for thebarrier layer have low permeability such as Saran® film (poly(vinylidene chloride), Barex® resin (acyrlonitrile-co-methyl acrylate),poly (vinyl alcohol), and PET film (polyethylene terephthalate). The'294 patent does not disclose core layers having different hardnessgradients.

Sullivan, Ladd, and Hebert, U.S. Pat. No. 7,708,654 discloses a golfball having a foamed intermediate layer. Referring to FIG. 1 in the '654patent, the golf ball includes a core (12), an intermediate layer (14)made of a highly neutralized polymer having a reduced specific gravity(less than 0.95), and a cover (16). According to the '654 patent, theintermediate layer can be an outer core, a mantle layer, or an innercover. The reduction in specific gravity of the intermediate layer iscaused by foaming the composition of the layer and this reduction can beas high as 30%. The '654 patent discloses that other foamed compositionssuch as foamed polyurethanes and polyureas may be used to form theintermediate layer.

Tutmark, U.S. Pat. No. 8,272,971 is directed to golf balls containing anelement that reduces the distance of the ball's flight path. In oneembodiment, the ball includes a core and cover. A cavity is formedbetween core and cover and this may be filled by a foamed polyurethane“middle layer” in order to dampen the ball's flight properties. The foamof the middle layer is relatively light in weight; and the core isrelatively heavy and dense. According to the '971 patent, when a golferstrikes the ball with a club, the foam in the middle layer actuates andcompresses, thereby absorbing much of the impact from the impact of theball.

Although some foam core constructions for gold balls have beenconsidered over the years, there are drawbacks with using many foammaterials. For example, one drawback with some polyurethane foams isthey may have relatively low thermal-stability. That is, some of thesefoam compositions do not have good heat-resistance and may degrade whenexposed to high temperatures. To make finished golf balls containingfoam cores, a thermoplastic or thermoset composition, for example,polybutadiene rubber, is molded over the foam material. In such moldingoperations, a substantial level of heat and pressure is applied to thecore structure. If the foam inner core does not have goodthermal-stability, the foam may collapse on itself. The chemical andphysical properties of the foam composition may change and theproperties of the resulting golf ball core may be adversely affected.For example, there may be a negative impact on the size, resiliency, andstiffness of the foam core.

In view of some of the disadvantages with some golf ball foam cores, itwould be desirable to have foam cores with high heat stability. The foamcores also should have good resiliency, rebounding performance, anddurability. The present invention provides new foam core compositionsand constructions having such properties as well as other advantageousfeatures and benefits. The present invention also provides siliconeelastomer compositions having high elongation, tensile strength,chemical/fluid-resistance, and weatherability properties. Thesecompositions can be used to form any layer (for example, core,intermediate, or cover) in the golf ball. The invention also encompassesgolf balls containing such improved core, intermediate, and cover layerconstructions.

SUMMARY OF THE INVENTION

The present invention provides a multi-piece golf ball comprising asolid core assembly having at least one layer and a cover having atleast one layer. In one version, the golf ball includes: i) an innercore (center), preferably formed from a polybutadiene rubbercomposition; ii) an inner cover layer comprising a non-foamed siliconeelastomer composition, and iii) an outer cover layer disposed about theinner cover layer. Preferably, the silicone elastomer composition isformed using at least one heterobifunctional macromer, and thecomposition has an elongation greater than 2000%, more preferablygreater than 3000%. The inner cover layer preferably has a midpointhardness in the range of about 10 to about 60 Shore A. The outer coverlayer preferably has a surface hardness in the range of about 55 toabout 75 Shore D. In one preferred embodiment, the inner cover layer hasa midpoint hardness in the range of about 25 to about 54 Shore A; andthe outer cover layer has a surface hardness in the range of about 58 toabout 71 Shore A. Preferably, the surface hardness of the outer coverlayer is greater than the midpoint hardness of the inner cover layer. Inanother embodiment, the midpoint hardness of the inner cover layerformed from the silicone elastomer composition is greater than thesurface hardness of the outer cover layer. For example, the siliconeelastomer inner cover may have a midpoint hardness in the range of about50 to about 75 Shore A; and the outer cover layer may have a surfacehardness in the range of about 20 to about 60 Shore D.

Thermoset or thermoplastic materials are used to form the inner core andouter cover layers of the golf balls in the present invention. In oneembodiment, the core comprises an inner core and surrounding outer corelayer, and at least one of the core layers is formed from a rubbercomposition. In one embodiment, the outer cover layer is formed from anethylene acid copolymer ionomer, wherein less than 70% or greater than70% of the acid groups have been neutralized. In another embodiment, theouter cover layer is formed from polyurethanes, polyureas,polyurethane-urea hybrids, and copolymers and blends thereof.

In yet another embodiment, a golf ball comprising an inner core layer,intermediate core layer, and outer core layer can be made. The innercore layer may comprise a thermoset rubber composition or athermoplastic composition such as an ethylene acid copolymer ionomer andhave a diameter in the range of about 0.100 to about 1.1000 inches. Theinner core preferably has a positive hardness gradient. The intermediatecore layer may comprise a non-foamed silicone elastomer composition andhave a thickness in the range of about 0.050 to about 0.400 inches. Inone embodiment, the intermediate core layer has a zero or negativehardness gradient. In another embodiment, the intermediate core layerhas a positive hardness gradient. The outer core layer may comprise athermoset rubber composition or a thermoplastic composition and have adiameter in the range of about 0.200 to about 0.750 inches. The outercore layer also can have a zero/negative hardness gradient or a positivehardness gradient.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features that are characteristic of the present invention areset forth in the appended claims. However, the preferred embodiments ofthe invention, together with further objects and attendant advantages,are best understood by reference to the following detailed descriptionin connection with the accompanying drawings in which:

FIG. 1 is a perspective view of a spherical inner core made of a foamedcomposition in accordance with the present invention;

FIG. 2 is a perspective view of one embodiment of upper and lower moldcavities used to make the dual-layered cores of the present invention;

FIG. 3 is a cross-sectional view of a three-piece golf ball having adual-layered core made in accordance with the present invention;

FIG. 4 is a cross-sectional view of a four-piece golf ball having adual-layered core made in accordance with the present invention;

FIG. 5 is a partial cut-away perspective view of a three-layered corehaving inner, intermediate, and outer core layers made in accordancewith the present invention; and

FIG. 6 is a cross-sectional view of a four-piece golf ball having athree-layered core and single-layered cover made in accordance with thepresent invention.

DETAILED DESCRIPTION OF THE INVENTION

Golf Ball Constructions

Golf balls having various constructions may be made in accordance withthis invention. For example, golf balls having three piece, four-piece,and five-piece constructions with single or multi-layered covermaterials may be made. Representative illustrations of such golf ballconstructions are provided and discussed further below. The term,“layer” as used herein means generally any spherical portion of the golfball. More particularly, in one version, a three-piece golf ballcontaining a dual-layered core and single-layered cover is made. Thedual-core includes an inner core (center) and surrounding outer corelayer. In another version, a four-piece golf ball containing a dual-coreand dual-cover (inner cover and outer cover layers) is made. In yetanother construction, a four-piece or five-piece golf ball containing adual-core; casing layer(s); and cover layer(s) may be made. As usedherein, the term, “casing layer” means a layer of the ball disposedbetween the multi-layered core sub-assembly and cover. The casing layeralso may be referred to as a mantle or intermediate layer. The diameterand thickness of the different layers along with properties such ashardness and compression may vary depending upon the construction anddesired playing performance properties of the golf ball.

Inner Core Composition

In general, silicone foam compositions are made by forming gas bubblesin a polymer mixture using a foaming (blowing) agent. As the bubblesform, the mixture expands and forms a foam composition that can bemolded into an end-use product having either an open or closed cellularstructure. Flexible foams generally have an open cell structure, wherethe cells walls are incomplete and contain small holes through whichliquid and air can permeate. Such flexible foams are used traditionallyfor automobile seats, cushioning, mattresses, and the like. Rigid foamsgenerally have a closed cell structure, where the cell walls arecontinuous and complete, and are used for used traditionally forautomobile panels and parts, building insulation and the like. Manyfoams contain both open and closed cells. It also is possible toformulate flexible foams having a closed cell structure and likewise toformulate rigid foams having an open cell structure.

As described in Daniel Klempner and Kurt C. Firsch, eds., Handbook ofPolymeric Foams and Foam Technology, (Munich, Vienna, New York,Barcelona: Hanser Publishers, 1991), silicone foams are generallyproduced by the condensation reaction between SiH and SiOH as shownbelow.SiH+SiOH+catalyst→SiOSi+H

When these two components are mixed together, they generate hydrogen gaswhich causes bubbles to form within the composition. The gas becomestrapped in cells to produce foam. During the curing step, the “liquidfoam” (mixed liquid reactants) are transformed into a solid material.These reactions can occur at room temperature, when the three necessarycomponents (SiH-containing cross-linker, SiOH-containing polymer, andcatalyst) are mixed together. These foams can be considered two-partsystems (the SiH-containing cross-linker makes up one component; and theSiOH-containing polymer and catalyst make-up the second component.) Avariety of catalysts including tin, zinc, and platinum-based compounds,can be used to promote these reactions.

In the present invention, the inner core (center) comprises alightweight foam silicone composition. The foam may have an open orclosed cellular structure or combinations thereof and the foam structuremay range from a relatively rigid foam to a very flexible foam.Referring to FIG. 1, a foamed inner core (4) having a geometric center(6) and outer skin (8) may be prepared in accordance with thisinvention.

As discussed above, hydrogen gas, which evolves as during the reactions,is the most common foaming (blowing) agent used to make silicone foam.However, other foaming agents may be introduced into the polymerformulation to generate the foam cells. In general, there are two typesof foaming agents: physical foaming agents and chemical foaming agents.

Physical Foaming Agents.

These foaming agents typically are gasses that are introduced under highpressure directly into the polymer composition. Chlorofluorocarbons(CFCs) and partially halogenated chlorofluorocarbons are effective, butthese compounds are banned in many countries because of theirenvironmental side effects. Alternatively, aliphatic and cyclichydrocarbon gasses such as isobutene and pentane may be used. Inertgasses, such as carbon dioxide and nitrogen, also are suitable.

Chemical Foaming Agents.

These foaming agents typically are in the form of powder, pellets, orliquids and they are added to the composition, where they decompose orreact during heating and generate gaseous by-products (for example,nitrogen or carbon dioxide). The gas is dispersed and trapped throughoutthe composition and foams it.

Hydroxyl-containing materials that react with some of the SiH-containingcross-linker during the silicone-forming reaction are preferred blowingagents. Different sources of hydroxyl groups may be used including waterand alcohols. Hydroxyl-containing polysiloxanes also can be used. Otherchemical blowing agents include inorganic compounds, such as ammoniumcarbonate and carbonates of alkalai metals, or may organic compounds,such as azo and diazo compounds, such as nitrogen-based azo compounds.Suitable azo compounds include, but are not limited to,2,2′-azobis(2-cyanobutane), 2,2′-azobis(methylbutyronitrile),azodicarbonamide, p,p′-oxybis(benzene sulfonyl hydrazide), p-toluenesulfonyl semicarbazide, p-toluene sulfonyl hydrazide. Other foamingagents include any of the Celogens® sold by Crompton ChemicalCorporation, and nitroso compounds, sulfonylhydrazides, azides oforganic acids and their analogs, triazines, tri- and tetrazolederivatives, sulfonyl semicarbazides, urea derivatives, guanidinederivatives, and esters such as alkoxyboroxines. Also, foaming agentsthat liberate gasses as a result of chemical interaction betweencomponents such as mixtures of acids and metals, mixtures of organicacids and inorganic carbonates, mixtures of nitriles and ammonium salts,and the hydrolytic decomposition of urea may be used. As discussedabove, other hydroxyl-containing materials such as water andalcohol-based materials may be used.

Commercially-available silicone foam compositions that can be used inaccordance with this invention include, for example, silicone foamsavailable from Dow Corning Corp. (Midland, Mich.); Rogers Corp (CarolStream, Ill.); and Saint Gobain Performance Plastics (Hoosick Falls,N.Y.). In addition to the foaming agent as discussed above, the foamcomposition also may include other ingredients such as, for example,fillers, cross-linking agents, chain extenders, surfactants, dyes andpigments, coloring agents, fluorescent agents, adsorbents, stabilizers,softening agents, impact modifiers, antioxidants, antiozonants, and thelike.

Fillers.

The silicone foam composition may contain fillers such as, for example,mineral filler particulate. Suitable mineral filler particulates includecompounds such as zinc oxide, limestone, silica, mica, barytes,lithopone, zinc sulfide, talc, calcium carbonate, magnesium carbonate,clays, powdered metals and alloys such as bismuth, brass, bronze,cobalt, copper, iron, nickel, tungsten, aluminum, tin, precipitatedhydrated silica, fumed silica, mica, calcium metasilicate, bariumsulfate, zinc sulfide, lithopone, silicates, silicon carbide,diatomaceous earth, carbonates such as calcium or magnesium or bariumcarbonate, sulfates such as calcium or magnesium or barium sulfate.Silicon dioxides are particularly preferred because they are based onSi—O bonds and these materials are compatible with the Si—O—Si backboneof the silicone foam. Adding fillers to the composition provides manybenefits including helping improve the stiffness and strength of thecomposition. The mineral fillers tend to help decrease the size of thefoam cells and increase cell density. The mineral fillers also tend tohelp improve the physical properties of the foam such as hardness,compression set, and tensile strength.

More particularly, clay particulate fillers, such as Garamite® mixedmineral thixotropes and Cloisite® and Nanofil® nanoclays, commerciallyavailable from Southern Clay Products, Inc., and Nanomax® and Nanomer®nanoclays, commercially available from Nanocor, Inc may be used. Othernano-scale materials such as nanotubes and nanoflakes also may be used.Also, talc particulate (e.g., Luzenac HAR® high aspect ratio talcs,commercially available from Luzenac America, Inc.), glass (e.g., glassflake, milled glass, and microglass), and combinations thereof may beused. Metal oxide fillers have good heat-stability and include, forexample, aluminum oxide, zinc oxide, tin oxide, barium sulfate, zincsulfate, calcium oxide, calcium carbonate, zinc carbonate, bariumcarbonate, tungsten, tungsten carbide, and lead silicate fillers. Thesemetal oxides and other metal fillers such as, for example, particulate;powders; flakes; and fibers of copper, steel, brass, tungsten, titanium,aluminum, magnesium, molybdenum, cobalt, nickel, iron, lead, tin, zinc,barium, bismuth, bronze, silver, gold, and platinum, and alloys andcombinations thereof may be added to the silicone foam composition.

Surfactants.

The silicone foam composition also may contain surfactants to stabilizethe foam and help control the foam cell size and structure. In onepreferred version, the foam composition includes silicone surfactantwhich is very compatible with the silicone foam system. In general, thesilicone surfactant helps regulate the foam cell size and stabilizes thecell walls to prevent the cells from collapsing. As discussed above, theliquid reactants react to form the foam rapidly. The “liquid” foamdevelops into solid silicone foam in a relatively short period of time.If a silicone surfactant is not added, the gas-liquid interface betweenthe liquid reactants and expanding gas bubbles may not support thestress. As a result, the cell window can crack or rupture and there canbe cell wall drainage. In turn, the foam can collapse on itself. Addinga silicone surfactant helps create a surface tension gradient along thegas-liquid interface and helps reduce cell wall drainage. The siliconesurfactant has a relatively low surface tension and thus can lower thesurface tension of the foam. It is believed the silicone surfactantorients itself the foam cell walls and lowers the surface tension tocreate the surface tension gradient. Blowing efficiency and nucleationare supported by adding the silicone surfactant and thus more bubblesare created in the system. The silicone surfactant also helps create agreater number of smaller sized foam cells and increases the closed cellcontent of the foam due to the surfactant's lower surface tension. Thus,the cell structure in the foam is maintained as the as gas is preventedfrom diffusing out through the cell walls. Along with the decrease incell size, there is a decrease in thermal conductivity. The resultingfoam material also tends to have greater compression strength andmodulus. These improved physical properties may be due to the increasein closed cell content and smaller cell size.

As discussed further below, in one preferred embodiment, the specificgravity (density) of the foam inner core is less than the specificgravity of the outer core. If mineral filler or other additives areincluded in the foam composition, they should not be added in an amountthat would increase the specific gravity (density) of the foam innercore to a level such that it would be greater than the specific gravityof the outer core layer. If the ball's mass is concentrated towards theouter surface (for example, outer core layers), and the outer core layerhas a higher specific gravity than the inner core, the ball has arelatively high Moment of Inertia (MOI). In such balls, most of the massis located away from the ball's axis of rotation and thus more force isneeded to generate spin. These balls have a generally low spin rate asthe ball leaves the club's face after contact between the ball and club.Such core structures (wherein the specific gravity of the outer core isgreater than the specific gravity of the inner core) is preferred in thepresent invention. Thus, in one preferred embodiment, the concentrationof mineral filler particulate in the foam composition is in the range ofabout 0.1 to about 9.0% by weight.

Properties of Silicone Foams

The silicone foam compositions of this invention have numerous chemicaland physical properties making them suitable for core assemblies in golfballs.

The density of the foam is an important property and is defines as theweight per unit volume (typically, g/cm³) and can be measured per ASTMD-1622. The hardness, stiffness, and load-bearing capacity of the foamare independent of the foam's density, although foams having a highdensity typically have high hardness and stiffness. Normally, foamshaving higher densities have higher compression strength. Surprisingly,the foam compositions used to produce the inner core of the golf ballsper this invention have a relatively low density; however, the foams arenot necessarily soft and flexible, rather, they may be relatively firm,rigid, or semi-rigid depending upon the desired golf ball properties.Tensile strength, tear-resistance, and elongation generally refer to thefoam's ability to resist breaking or tearing, and these properties canbe measured per ASTM D-1623. The durability of foams is important,because introducing fillers and other additives into the foamcomposition can increase the tendency of the foam to break or tearapart. In general, the tensile strength of the foam compositions of thisinvention is in the range of about 20 to about 1000 psi (parallel to thefoam rise) and about 50 to about 1000 psi (perpendicular to the foamrise) as measured per ASTM D-1623 at 23° C. and 50% relative humidity(RH). Meanwhile, the flex modulus of the foams of this invention isgenerally in the range of about 5 to about 45 kPa as measured per ASTMD-790, and the foams generally have a compressive modulus of 200 to50,000 psi.

In another test, compression strength is measured on an Instron machineaccording to ASTM D-1621. The foam is cut into blocks and thecompression strength is measured as the force required to compress theblock by 10%. In general, the compressive strength of the foamcompositions of this invention is in the range of about 100 to about1800 psi (parallel and perpendicular to the foam rise) as measured perASTM D-1621 at 23° C. and 50% relative humidity (RH). The test isconducted perpendicular to the rise of the foam or parallel to the riseof the foam. The Percentage (%) of Compression Set also can be used.This is a measure of the permanent deformation of a foam sample after ithas been compressed between two metal plates under controlled time andtemperature condition (standard—22 hours at 70° C. (158° F.)). The foamis compressed to a thickness given as a percentage of its originalthickness that remained “set.” Preferably, the Compression Set of thefoam is less than ten percent (10%), that is, the foam recovers to apoint of 90% or greater of its original thickness.

In addition, the silicone foams have high thermal-stability. Thus, thefoam can resist changes to its structure and physical properties as thetemperature increases. The silicone foam can withstand high temperaturefor extended time periods without substantial decreases in chemical andphysical properties. In general, many silicone foams can withstandtemperatures in the range of about −100° F. (73° C.) to about 500° F.(260° C.). These heat-resistant properties are particularly importantduring the molding operation, where substantial heat and pressure areapplied to the mold cavities and molding process temperatures may varyover a wide range. As discussed further below, an outer corethermoplastic or thermoset layer is molded over the silicone foam core.A single or multi-layered cover is molded over this core structure.During these molding steps, it is important the core composition doesnot melt or thermally degrade. The foam composition must be able tohold-up under high temperatures so that its chemical and physicalproperties are not adversely affected. The cores comprising the siliconefoam compositions of this invention have high heat-stability. The coresshow improved heat-stability without sacrificing properties such asresiliency and durability.

The thermal stability of the above silicone foam composition can bemeasured by thermogravimetry. Preferably, the foam composition has aweight loss at 250° C., based on the weight of the mixture at 25° C., ofpreferably not more than 5 wt. %, more preferably not more than 4 wt. %,and even more preferably not more than 1 wt. %.

It should be noted that silicone sponge rubber, silicone solid rubber,and silicone foam rubber are different materials having differentproperties and appearances. In general, manufacturing silicone spongeand solid rubber involves processing a gum-type silicone materialthrough hard-pressure calendar rollers. The silicone material is thenrun through a curing apparatus that continuously vulcanizes the spongerubber. Such silicone sponge and solid rubber materials are described inSullivan, Keller, and Binette, U.S. Pat. No. 7,384,349. In contrast,silicone foam rubber is made from liquid components that are mixedtogether and cured.

As discussed above, to make silicone foam rubber, the first component(Component A) generally consists of SiOH-containing compound andcatalyst; and the second component (Component B) generally consists ofthe SiH-containing compound. These liquid components are metered to amixing chamber, where the components are mixed using a mechanical mixeror static mixer. Alternatively, the components can be manually mixedtogether. An exothermic reaction occurs when the ingredients are mixedtogether and this continues as the reactive mixture is dispensed intothe mold cavities (otherwise referred to as half-molds or mold cups).The mold cavities may be referred to as first and second, or upper andlower, mold cavities. The mold cavities preferably are made of metalsuch as, for example, brass or silicon bronze.

Referring to FIG. 2, the mold cavities are generally indicated at (9)and (10). The lower and upper mold cavities (9, 10) are placed in lowerand upper mold frame plates (11, 12). The frame plates (11, 12) containguide pins and complementary alignment holes (not shown in drawing). Theguide pins are inserted into the alignment holes to secure the lowerplate (11) to the upper plate (12). The lower and upper mold cavities(9, 10) are mated together as the frame plates (11, 12) are fastened.When the lower and upper mold cavities (9, 10) are joined together, theydefine an interior spherical cavity that houses the spherical core. Theupper mold contains a vent or hole (14) to allow for the expanding foamto fill the cavities uniformly. A secondary overflow chamber (16), whichis located above the vent (14), can be used to adjust the amount of foamoverflow and thus adjust the density of the core structure being moldedin the cavities. As the lower and upper mold cavities (9, 10) are matedtogether and sufficient heat and pressure is applied, the foamedcomposition cures and solidifies to form a relatively rigid andlightweight spherical core. The resulting cores are cooled and thenremoved from the mold.

Both the silicone sponge rubber and silicone foam rubber are cellular innature. However, the silicone sponge rubber tends to have a higherdensity, higher tensile strength, and higher material weight versus thesilicone foam rubber. Because the silicone foam rubber generallycontains more air, it is generally softer and lower in density thansilicone sponge rubber. The silicone foam rubber also has bettercompression set properties than the silicone sponge rubber.

Non-Foam Silicones

Non-Foam silicone compositions also may be used in accordance with thepresent invention. In general, non-foam silicone polymers are availablein a wide variety of forms including, for example, fluids,elastomers/rubbers, gels, resins, and mixtures thereof. The siliconepolymers are based on a structure consisting of alternate silicon andoxygen atoms with various organic radicals attached to the silicon atom(for example, R1 and R2 can be methyl, vinyl, phenyl, or other groups)and the molecular weight of the silicone can vary based on the type ofproduct (for example, n can be in the range of 100 to 15,000) as shownin the structure below:

In general, non-foam silicones have many desirable properties includinggood thermal and oxidative stability. The non-foam silicones are stableover a wide range of temperature. These silicones have goodchemical/fluid-resistance, water-repellency, and can withstand differentweathering elements. The high stability and binding energy of thesiloxane bonds (—Si—O—Si—) helps impart these properties to thesesilicones. The silicones can be in the form of liquids, semisolids, orsolids depending on molecular weight and degree of polymerization. Themolecular structure of the silicones can vary and include linear,branched, cyclic, and cross-linked structures.

In one preferred embodiment, a non-foam silicone elastomer is used inaccordance with this invention. The non-foam silicone elastomer isgenerally formed by reacting a silicone polymer and cross-linking agent.The non-foamed silicone elastomer typically also contains fillers. Theproduction of non-foamed silicone elastomers and their resultingproperties are described further below.

The non-foam silicone compositions of this invention may be used in oneor more core, intermediate, or cover layers. For instance, in athree-layered core structure, the non-foam silicone elastomercomposition may be used to form the innermost core or center layer, orintermediate core layer, or outermost core layer. In another example, ina four-piece ball having a dual-layered core and dual-layered cover(inner and outer cover layers), the silicone-comprising composition maybe used to form the inner cover layer. The silicone-comprisingcompositions are thermoplastic and may be used to form layers that areadjacent to another layer made from a thermoplastic composition or maybe adjacent to a layer made from a thermosetting composition. Forexample, in a three (3) or more layered-core construction, the centermay be made from a thermosetting rubber composition, the intermediatecore layer may comprise the silicone-based composition, and the outercore layer may be made from a thermosetting rubber composition.Alternatively, the center and intermediate core layer may comprise athermosetting rubber and the outer core layer may comprise thethermoplastic silicone-based composition, and the like. These differentembodiments are described further below.

The non-foam silicone elastomers also may be used as an additive inthermoset rubber compositions used to make core, cover, or other layersof the golf ball of this invention. Suitable rubber compositions thatcan be used to make such core or other layers include, for example,polybutadiene, polyisoprene, ethylene propylene rubber (“EPR”),ethylene-propylene-diene (“EPDM”) rubber, and styrene-butadiene rubberand these rubbers are described further below. The silicone elastomer ispreferably added to the thermoset rubber composition in an amount of 1to 80 parts per hundred (pph).

Furthermore, the non-foam silicone elastomers may be used to modifythermoplastic polymer compositions that are used to make core, cover, orother layers. For example, the non-foam silicone elastomers may be addedto thermoplastic polyurethane (TPU) compositions.

Core Construction

As discussed above, in some examples, thermoplastic and thermosetmaterials may be used to construct core assemblies having three layersas described in the following Table I. In these examples, a thermosetmaterial is used to form the inner core (center) and the siliconecomposition of this invention is preferably used to form theintermediate and/or outer core layers.

TABLE I Thermoset Inner Core in Three-Layered Core Assemblies Inner CoreIntermediate Core Layer Outer Core Layer Thermoset material Non-FoamSilicone Thermoset material material Thermoset material Thermosetmaterial Non-Foam Silicone material Thermoset material Non-Foam SiliconeThermoplastic material material Thermoset material Thermoplasticmaterial Non-Foam Silicone material

In yet other examples, the thermoplastic and thermoset materials may beused to construct core assemblies having three layers as described inthe following Table II. In these examples, a thermoplastic material isused to form the inner core (center) and the silicone composition ofthis invention is preferably used to form the intermediate and/or outercore layers.

TABLE II Thermoplastic Inner Core in Three-Layered Core Assemblies InnerCore Intermediate Core Layer Outer Core Layer Thermoplastic materialNon-Foam Silicone Thermoset material material Thermoplastic materialNon-Foam Silicone Thermoplastic material material Thermoplastic materialThermoplastic material Non-Foam Silicone material Thermoplastic materialThermoset material Non-Foam Silicone material

In another example, where a three-layered cover construction is used,the non-foam silicone composition can be used to form an inner, orintermediate, or outermost cover layer. For example in a golf ballhaving a three-layered cover, the silicone-based composition may be usedto form any of the three layers, but preferably is used to form theinner or intermediate cover layer, or both. In a three-piece ball havinga dual-layered core (inner core and outer core layers) and surroundingouter cover, the silicone-based composition may be used to form theouter core layer. In a two-piece construction comprising a core and acover, either the core or cover or both layers may consist of thesilicone-based composition.

In yet other example, the foamed silicone composition of this inventionis used to form one layer, for example, the inner core of the golf ball;and the non-foamed silicone elastomer composition of this invention isused to form a second layer, for example, the inner cover of the golfball. The foamed silicone composition and non-foamed silicone elastomercompositions also can be used to form adjoining layers in the golf ball(for example, inner core and intermediate core layers in a multi-layeredcore construction.) The foamed silicone and non-foamed siliconeelastomer compositions of this invention can be used to form anylayer(s) in the golf ball construction.

As discussed above, the core preferably has a multi-layered structurecomprising an inner core, intermediate core layer, and outer core layer.In FIG. 5, a partial cut-away view of one version of the core (42) ofthis invention is shown. The core (42) includes an inner core (44)comprising a thermoset composition; an intermediate core layer (46)comprising the non-foam silicone elastomer composition of thisinvention; and an outer core layer (48) comprising a thermosetcomposition. As shown in FIG. 5, the intermediate core layer (46) isdisposed about the inner core (44), and the outer core layer (48)surrounds the intermediate core layer. The hardness of the coresub-assembly (inner core, intermediate core layer, and outer core layer)is an important property. In general, cores with relatively highhardness values have higher compression and tend to have good durabilityand resiliency. However, some high compression balls are stiff and thismay have a detrimental effect on shot control and placement. Thus, theoptimum balance of hardness in the core sub-assembly needs to beattained. In FIG. 6, a cross-sectional view of one version of afour-piece golf ball (50) that can be made in accordance with thisinvention is illustrated. The ball (50) contains a multi-layered corehaving an inner core (52), intermediate core layer (54), and outer corelayer (56) surrounded by a single-layered cover (60).

As described in the above Tables, in one embodiment, the inner core andouter core layers comprise thermoset materials, while the intermediatecore layer comprises the silicone composition of this invention.Suitable thermoset materials that may be used to form the inner core andouter core layer include, but are not limited to, polybutadiene,polyisoprene, ethylene propylene rubber (“EPR”),ethylene-propylene-diene (“EPDM”) rubber, styrene-butadiene rubber,styrenic block copolymer rubbers (such as “SI”, “SIS”, “SB”, “SBS”,“SIBS”, and the like, where “S” is styrene, “I” is isobutylene, and “B”is butadiene), polyalkenamers such as, for example, polyoctenamer, butylrubber, halobutyl rubber, polystyrene elastomers, polyethyleneelastomers, polyurethane elastomers, polyurea elastomers,metallocene-catalyzed elastomers and plastomers, copolymers ofisobutylene and p-alkylstyrene, halogenated copolymers of isobutyleneand p-alkylstyrene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, and blends of two or morethereof. Other additives and fillers for the rubber compositions aredescribed further below. The thermoset rubber materials may be curedusing a conventional curing process also described further below.Suitable curing processes include, for example, peroxide-curing,sulfur-curing, high-energy radiation, and combinations thereof.Preferably, the rubber composition contains a free-radical initiatorselected from organic peroxides, high energy radiation sources capableof generating free-radicals, and combinations thereof.

In other embodiments, also as described in the above Tables,thermoplastic materials such as highly-neutralized polymer compositions(HNPs) may be used to form any core layer in accordance with the presentinvention. In one embodiment, the inner core and outer core layerscomprise thermoplastic materials, while the intermediate core layercomprises the silicone composition of this invention. Suitable HNPcompositions comprise an HNP and optionally melt-flow modifier(s),additive(s), and/or filler(s). For purposes of the present disclosure,“HNP” refers to an acid polymer after at least 70%, preferably at least80%, more preferably at least 90%, more preferably at least 95%, andeven more preferably 100%, of the acid groups present are neutralized.HNPs are discussed further below. It is understood that the HNP may be ablend of two or more HNPs. Preferred acid polymers are copolymers of anα-olefin and a C₃-C₈ α,β-ethylenically unsaturated carboxylic acid,optionally including a softening monomer. The α-olefin is preferablyselected from ethylene and propylene. The acid is preferably selectedfrom (meth) acrylic acid, ethacrylic acid, maleic acid, crotonic acid,fumaric acid, and itaconic acid. (Meth) acrylic acid is particularlypreferred. The optional softening monomer is preferably selected fromalkyl (meth) acrylate, wherein the alkyl groups have from 1 to 8 carbonatoms. Preferred acid copolymers include, but are not limited to, thosewherein the α-olefin is ethylene, the acid is (meth) acrylic acid, andthe optional softening monomer is selected from (meth) acrylate, n-butyl(meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, andethyl (meth) acrylate. Particularly preferred acid copolymers include,but are not limited to, ethylene/(meth) acrylic acid/n-butyl acrylate,ethylene/(meth) acrylic acid/methyl acrylate, and ethylene/(meth)acrylic acid/ethyl acrylate.

The inner core preferably has a diameter in the range of about 0.100 toabout 1.250 inches. For example, the inner core may have a diameterwithin a range of about 0.100 to about 1.100 inches. In another example,the inner core may have a diameter within a range of about 0.300 toabout 0.800 inches. In yet another example, the inner core may have adiameter within a range of about 1.000 to about 1.250 inches. Meanwhile,the intermediate core layer preferably has a thickness in the range ofabout 0.010 to about 0.095 inches. More particularly, in one example,the thickness of the intermediate core layer is within a range of about0.025 to about 0.065 inches. In another embodiment, the intermediatecore layer has a thickness within a range of about 0.030 to about 0.060inches. As far as the outer core layer is concerned, it preferably has athickness in the range of about 0.100 to about 0.750 inches. Forexample, the outer core layer may have a thickness in the range of about0.200 to about 0.600 inches or about 0.300 to about 0.500 inches. Theoverall diameter of the core sub-assembly (inner, intermediate, andouter core layers) is preferably in the range of about 1.450 to about1.700 inches, or is preferably in the range of about 1.450 to about1.620 inches.

The inner core preferably has a geometric center hardness(H_(inner core center)) of about 20 Shore C or greater; for example, theH_(inner core center) may have a hardness in the range of about 20 toabout 85 Shore C. In another example, the hardness is in the range ofabout 30 to about 70 Shore C or more particularly in the range of about40 to about 60 Shore C. Concerning the outer surface hardness of theinner core (H_(inner core surface)), this hardness is preferably about25 to about 90 Shore C. In one example, the H_(inner core surface) is inthe range of about 40 to about 80 Shore C, and more particularly in therange of about 50 to about 75 Shore C.

Meanwhile, the intermediate core layer preferably has an outer surfacehardness (H_(outer surface of the Inter Core)) of about 20 Shore D orgreater, and more particularly within a range of about 20 to about 55Shore D. Preferably, the H_(outer surface of the Inter Core) is lessthan 55 Shore D and in the range of about 20 to 50 Shore D, moreparticularly in the range of about 25 to about 45 Shore D. The outersurface hardness of the intermediate core layer(H_(outer surface of the Inter Core)), as measured in Shore C units,preferably has a lower limit of about 30 Shore C, and an upper limit ofabout 85 Shore C. Preferably, the H_(outer surface of the Inter Core) isless than 85 Shore C and in the range of about 30 to 80 Shore C, moreparticularly in the range of about 40 to about 75 Shore C. While, themidpoint (or inner surface) hardness of the intermediate core(H_(midpoint of the Inter Core)) preferably is about 25 Shore D orgreater and more preferably is within a range of about 25 to about 60Shore D. As measured in Shore C units, the midpoint hardness of theintermediate core (H_(midpoint of the Inter Core)) preferably has alower limit of about 35 Shore C and an upper limit of about 90 Shore C.The outer surface hardness of the intermediate core layer(H_(outer surface of the Inter Core)), as measured in Shore A units,preferably has a lower limit of about 10 Shore A, and an upper limit ofabout 90 Shore A. While, the midpoint (or inner surface) hardness of theintermediate core (H_(midpoint of the Inter Core)) also preferably has ahardness with a lower limit of about 10 Shore A, and an upper limit ofabout 90 Shore A.

In one preferred example, the intermediate core layer is formed from asilicone elastomer composition. The intermediate layer has an outersurface hardness and midpoint hardness. In this intermediate core layer,the outer surface hardness can be the same or less than the midpointhardness to provide a zero or negative hardness gradient. For example,the midpoint hardness can be in the range of about 37 to about 80 ShoreA, or about 50 to about 70 Shore A; and the outer surface hardness canbe in the range of about 30 to about 73 Shore A, or about 40 to about 60Shore A to provide a zero or negative hardness gradient across theintermediate core. Alternatively, in this intermediate core layer, theouter surface hardness can be greater than the midpoint hardness toprovide a positive hardness gradient. For example, the midpoint hardnesscan be in the range of about 15 to about 80 Shore A, or about 20 toabout 70 Shore A, or about 40 to about 62 Shore A; and the outer surfacehardness can be in the range of about 27 to about 87 Shore A, or about50 to about 70 Shore A to provide a positive hardness gradient acrossthe intermediate core.

On the other hand, the outer core layer preferably has an outer surfacehardness (H_(outer surface of OC)) of about 40 Shore D or greater, andmore preferably within a range of about 40 to about 80 Shore D. Theouter surface hardness of the outer core layer(H_(outer surface of OC)), as measured in Shore C units, preferably hasa lower limit of about 45 Shore C, and an upper limit of about 85 ShoreC. And, the inner surface of the outer core layer(H_(inner surface of OC)) or midpoint hardness of the outer core layer(H_(midpoint of OC)), preferably has a hardness of about 40 Shore D orgreater, and more preferably within a range having a lower limit ofabout 42 and an upper limit of about 82 Shore D. The inner surfacehardness (H_(inner surface of OC)) or midpoint hardness(H_(midpoint of OC)) of the outer core layer, as measured in Shore Cunits, preferably has a lower limit of about 44 and an upper limit ofabout 80 Shore C.

The midpoint of a core layer is taken at a point equidistant from theinner surface and outer surface of the layer to be measured, mosttypically an outer core layer. Once one or more core layers surround alayer of interest, the exact midpoint may be difficult to determine,therefore, for the purposes of the present invention, the measurement of“midpoint” hardness of a layer is taken within plus or minus 1 mm of themeasured midpoint of the layer.

In one embodiment, the outer surface hardness of the outer core layer(H_(outer surface of OC)), is less than the outer surface hardness(H_(inner core surface)) or midpoint hardness (H_(midpoint of OC)), ofthe inner core by at least 3 Shore C units and more preferably by atleast 5 Shore C.

In a second embodiment, the outer surface hardness of the outer corelayer (H_(outer surface of OC)), is greater than the outer surfacehardness (H_(inner core surface)) or midpoint hardness(H_(midpoint of OC)), of the inner core by at least 3 Shore C units andmore preferably by at least 5 Shore C.

As discussed above, in one preferred version, the inner core is formedfrom a polybutadiene rubber or other thermoset rubber composition andthe outer core layer is formed from a polybutadiene rubber or otherthermoset rubber composition. In another preferred version, the innerand outer core layers are each formed from a thermoplastic composition,particularly an ethylene acid copolymer ionomer composition.

The core structure also has a hardness gradient across the entire coreassembly. In one embodiment, the (H_(inner core center)) is in the rangeof about 10 Shore C to about 60 Shore C, preferably about 13 Shore C toabout 55 Shore C; and the (H_(outer surface of OC)) is in the range ofabout 65 to about 96 Shore C, preferably about 68 Shore C to about 94Shore C or about 75 Shore C to about 93 Shore C, to provide a positivehardness gradient across the core assembly. In another embodiment, thereis a zero or negative hardness gradient across the core assembly. Forexample, the center of the core (H_(inner core center)) may have ahardness gradient in the range of 20 to 90 Shore C; and the outersurface of the outer core may have a hardness gradient in the range of10 to 80 Shore C. The hardness gradient across the core assembly willvary based on several factors including, but not limited to, thedimensions of the inner core, and compositions of the inner core,intermediate core, and outer core layers.

Cover Construction

In another version, the inner cover layer is formed from thesilicone-based composition of this invention, and the outer cover layeris formed from a suitable thermoset or thermoplastic composition. Insuch instances, suitable materials that can be used to form the outercover layer include, for example, polyurethanes; polyureas; copolymers,blends and hybrids of polyurethane and polyurea; olefin-based copolymerionomer resins (for example, Surlyn® ionomer resins and DuPont HPF®1000, HPF® 2000, and HPF® 1035; and HPF® AD 1172, commercially availablefrom DuPont; Iotek® ionomers, commercially available from ExxonMobilChemical Company; Amplify® 10 ionomers of ethylene acrylic acidcopolymers, commercially available from The Dow Chemical Company; andClarix® ionomer resins, commercially available from A. Schulman Inc.);polyethylene, including, for example, low density polyethylene, linearlow density polyethylene, and high density polyethylene; polypropylene;rubber-toughened olefin polymers; acid copolymers, for example,poly(meth)acrylic acid, which do not become part of an ionomericcopolymer; plastomers; flexomers; styrene/butadiene/styrene blockcopolymers; styrene/ethylene-butylene/styrene block copolymers;dynamically vulcanized elastomers; copolymers of ethylene and vinylacetates; copolymers of ethylene and methyl acrylates; polyvinylchloride resins; polyamides, poly(amide-ester) elastomers, and graftcopolymers of ionomer and polyamide including, for example, Pebax®thermoplastic polyether block amides, commercially available from ArkemaInc; cross-linked trans-polyisoprene and blends thereof; polyester-basedthermoplastic elastomers, such as Hytrel®, commercially available fromDuPont or RiteFlex®, commercially available from Ticona EngineeringPolymers; polyurethane-based thermoplastic elastomers, such asElastollan®, commercially available from BASF; synthetic or naturalvulcanized rubber; and combinations thereof. Castable polyurethanes,polyureas, and hybrids of polyurethanes-polyureas are particularlydesirable because these materials can be used to make a golf ball havinghigh resiliency and a soft feel. By the term, “hybrids of polyurethaneand polyurea,” it is meant to include copolymers and blends thereof.

Polyurethanes, polyureas, and blends, copolymers, and hybrids ofpolyurethane/polyurea are also particularly suitable. When used as theouter cover layer material, polyurethanes and polyureas can be thermosetor thermoplastic. Thermoset materials can be formed into golf balllayers by conventional casting or reaction injection molding techniques.Thermoplastic materials can be formed into golf ball layers byconventional compression or injection molding techniques.

In one particularly preferred version, a two-layered cover is made. Forexample, a cover assembly having inner and outer cover layers, wherein arelatively hard outer cover is disposed about a relatively soft innercover may be made. Alternatively, a relatively soft outer cover may bedisposed about a relatively hard inner cover. The non-foamedsilicone-based composition of this invention may be used to form atleast one of the cover layers. Other thermoplastic or thermosetcompositions as described above may be used to form the other coverlayer in the two-layered cover assembly.

The thickness of the silicone-based inner cover is preferably in therange of about 0.010 to about 0.075 inches, more preferably about 0.015to about 0.045 inches, and most preferably about 0.020 to about 0.040inches. As discussed above, in one version, the silicone-based innercover can have a midpoint hardness in the range of about 10 to about 90Shore A or about 15 to about 60 Shore A, more preferably about 25 toabout 54 Shore A; and the outer cover can have an outer surface hardnessin the range of about 45 to about 80 Shore D or about 55 to about 75Shore D, more preferably about 58 to about 71 Shore D, wherein the outersurface hardness of the outer cover layer is greater than midpointhardness of the inner cover layer. The outer cover layer is preferablymade of a blend of ethylene acid copolymer ionomers (for example,Surlyn™ 8940/7940) and preferably has a thickness of about 0.015 inchesto about 0.020 to about 0.080 inches, more preferably about 0.030 toabout 0.060 inches. In this embodiment, the hardness of the outer coverlayer is preferably in the range of about 63 to about 67 Shore D.Surlyn™ 8940 is an E/MAA copolymer in which the acid groups have beenpartially neutralized with sodium ions. Surlyn™ 7940 is an E/MAAcopolymer in which the acid groups have been partially neutralized withlithium ions.

In another version, the silicone-based inner cover can have a midpointhardness in the range of about 10 to about 90 Shore A or about 15 toabout 80 Shore A, or about 30 to about 70 Shore A more preferably about35 to about 65 Shore A; and the outer cover can have an outer surfacehardness in the range of about 10 to about 70 Shore D or about 15 toabout 65 Shore D, more preferably about 20 to about 60 Shore D, whereinthe outer surface hardness of the outer cover layer is less thanmidpoint hardness of the inner cover layer. Referring to FIG. 7, afive-piece golf ball (62) containing a three-layered core having aninner core (64), intermediate core (66), and outer core layer (68) isshown. The multi-layered core is surrounded by a multi-layered coverhaving an inner cover layer (70) and outer cover layer (72).

In another particularly preferred version, a three-layered cover ismade. For example, a cover assembly having inner and outer cover layers,wherein an intermediate cover layer is disposed between the inner andouter cover layers, may be prepared. In such a construction, thesilicone-based compositions of this invention may be used to form atleast one of the inner, intermediate, or outer cover layers.

Properties of Non-Foam Silicone Elastomers

In general, raw, uncured silicone rubber contains polymers of differentchain lengths. Solid silicone rubber contains polymers of highermolecular weight and relatively long polymer chains. On the other hand,liquid silicone rubber contains polymers of lower molecular weight. Across-linking mechanism such as peroxide-curing or platinum catalystsystems are used to convert the raw, uncured silicone rubber into stablecured silicone elastomer. Fillers are used to reinforce the elasticsilicone network. Most silicone elastomer compositions are based onpolydimethyl siloxanes having the general chemical structure shownbelow:

The value of n varies mainly with the type of product. Forroom-temperature-vulcanizing products, n is in the 200-1,500 range; forheat-cured products, n is approximately 3,000-11,000. The physicalproperties of silicone elastomers are generally determined by the degreeof cross-linking in the material. Cross-linking silicone polymers ofappropriate molecular weight provides elastomeric properties. Fillersincrease strength through reinforcement, and extending fillers andadditives, for example, antioxidants, adhesion promoters, and pigments,can be used to provide specific properties.

The silicone elastomers have good temperature-resistance—the elastomerscan handle very low and very high temperatures (for example, in therange of −40° to 392° F.). The silicone elastomers are very flexible andare easy to process with good chemical/fluid-resistance. Also, theelastomers have good weatherability and in particular, they have goodozone and ultraviolet (UV) light-resistance.

Any suitable cross-linking system can be used for curing the siliconeelastomers including, but not limited to the following: a) byfree-radical crosslinking with, for example, benzoyl peroxide, throughthe formation of ethylenic bridges between chains; b) by cross-linkingof vinyl or allyl groups attached to silicon through reaction withsilylhydride groups; and c) by cross-linking linear or slightly branchedsiloxane chains having reactive end groups such as silanols. This yieldsSi—O—Si crosslinks. The latter mechanism forms the basis of the curingof room-temperature vulcanizing (RTV) silicone elastomers. These areavailable as two-part mixtures in which all three essential ingredientsfor the cure (silanol-terminated polymer, cross-linking agent such asethyl silicate, and a catalyst such as a tin soap) are combined at thetime the two components are mixed, and as one-part materials using ahydrolyzable polyfunctional silane or siloxane as crosslinker, activatedby atmospheric moisture.

The silicone elastomers are preferably reinforced by finely dividedfillers such as silica. For example, the finely divided silicas may bemade by fume or wet processes. The fume process provides the highestdegree of reinforcement. Accordingly, the particle size is small. Theparticle diameter should be about the length of a fully extended polymerchain, that is, about 1 μm, for semi-reinforcement and about 0.01-0.05μm for strong reinforcement. The fillers can be treated to give it anorganic or a silicone coating before mixing it with polymer.Hexamethyldisilazane, [(CH₃)Si]₂NH, is sometimes used as a couplingagent. Treating the silica particles with hot vapors of low molecularweight cyclic siloxanes reduces agglomeration and prevents prematurecrepe hardening. Non-reinforcing fillers, such as iron oxide or titaniumdioxide, may be utilized to stabilize or color the resulting siliconematerial or to decrease the cost per unit volume.

Various silicone elastomers can be used in accordance with the presentinvention. For example, silicone elastomers commercially-available fromDow Corning under the series “Thermal Radical Cure” (TRC) adhesives canbe used. More particularly, Dow Corning EA-7100™ silicone elastomeradhesive can be used. Other silicone polymers that can be used inaccordance with the present invention include high-consistency siliconerubbers and liquid silicone rubber. Liquid silicone rubber (LSR)compounds are two-part silicone materials that can be mixed, pumped, andrapidly heat-cured to form elastomeric components. High-consistencyrubber bases (HCR) can be blended with fillers, modifiers, vulcanizingagents, and pigments and heat-cured. The Degree of Polymerization (DP)and Molecular Weight (MW) of the LSR and HCR materials can vary. Forexample, the DP of the LSR materials can be in the range of 10 to 100;and the DP of the HCR materials can be in the range of 5,000 to 10,000.Also, for example, the MW of the LSR materials can be in the range of900 to 7,600; and the MW of the HCR materials can be in the range of370,000 to 740,000.

Typically, silicone elastomer materials have elongations of 100 to1,000% and tensile strengths of 500 to 1,000 psi. As discussed above,raw silicone rubber is cured to form silicone elastomers having theseelastomeric properties. Normally, peroxide-curing is used, where theperoxides decompose at elevated temperatures to form highly-reactiveradicals. These peroxide radicals chemically cross-link the polymerchains. Platinum-catalyzed addition curing also can be used. In thiscuring process, the Si—H groups react with vinyl groups of the polymerto form a three-dimensional network.

In recent years, a new class of silicone elastomers with high elongationand shape-recovery abilities has been developed. As described in thearticle, “Ultra-High Elongation Silicone Elastomers,” by B. Arkles, J.Goff, S. Sulaiman, and A. Sikorsky, Rubber World (June 2016) pp. 29-34,these silicone elastomers are produced by polymerization methods thatinvolve first forming heterobifunctional macromers. The macromerscontain a vinyl group and hydride group at opposite ends of thesiloxane. First, the macromere are formulated into silane elastomerbases by compounding with fillers, pigments, and reinforcing agents.Then, the formulated bases are converted to high molecular weightsilicone elastomers by platinum-catalyzed reactions. Suitable methodsfor forming such high elongation silicone elastomers are described inArkles et al., U.S. Pat. No. 9,145,474, the disclosure of which ishereby incorporated by reference. One preferred method for producingsuch silicone elastomers in the '474 patent comprises the steps of: (a)preparing a first mixture comprising a first telechelic siloxane and ahydrosilylation catalyst; (b) preparing a second mixture comprising asecond telechelic siloxane and a dual functional siloxane having twodifferent polymer termini; and (c) reacting the first mixture with thesecond mixture to produce the siloxane elastomer. This curing mechanisminvolves a step-growth polymerization resulting in the formation oflinear polymers having very high molecular weight. There may not be anycovalent crosslinking in the polymers. Rather, during thepolymerization, the flexible growing polymer chains may becomeentangled. The polymer chains become entangled within themselves andwith each other. This intra-chain or self-knotting of the polymers helpsthe polymers achieve extreme elongations.

The resulting high-elongation silicone elastomers have desirableproperties. For example, these silicone elastomers preferably haveelongations in the range of about 2,000 to about 7,000%; more preferablyin the range of about 3,000 to about 6,000%; and most preferably in therange of about 4,000 to about 5,000% (as measured per ASTM D412) andtensile strengths in the range of about 4 to 12 MPa; more preferably inthe range of about 6 to about 11 MPa; and most preferably in the rangeof about 8 to about 10 MPa (as measured per ASTM D412). In addition,these high elongation elastomers are relatively soft and have about 10to about 50 Shore A hardness, preferably about 15 to about 25 Shore Ahardness. These high elongation silicone elastomers also can be used inaccordance with the present invention. Suitable commercially-availablehigh elongation silicone elastomers include Gelest™ ExSil 100 andGelest™ RG-09, available from Gelest, Inc., (Morrisville, Pa. USA).Other suitable silicone elastomers are NuSil™ silicones available fromNuSil Technology, LLC (Carpinteria, Calif., USA). The properties of somesilicone elastomers are show below in below Tables III and IV.

TABLE III Mechanical and Physical Properties of Examples of CommercialHigh Elongation Silicone Elastomers. Gelest ™ Gelest ™ Property TestMethod ExSil 100 RG-09 Elongation D412 5,000%   4,600%   TensileStrength D412 8 to 9 MPa 9 to 10 MPa Tear Strength D624 — 40 to 42 kN/mElongation at — — 2,000%   Tear Failure Durometer Durometer 15% 15%(Shore A) Compression Set at —  5%  5% 22 hours at 23° C. ReboundResistance — 30% 30% Specific Gravity — 1.12 1.12

Gelest™ ExSil 100 and Gelest™ RG-09, are commercial high-elongationsilicone elastomers, available from Gelest, Inc., (Morrisville, Pa.USA). The property values in Table III are based on data reported in thearticle, “Ultra-High Elongation Silicone Elastomers,” by B. Arkles, J.Goff, S. Sulaiman, and A. Sikorsky, Rubber World (June 2016) pp. 29-34.

TABLE IV Mechanical and Physical Properties of Examples of CommercialHigh Elongation Silicone Elastomers Test Gelest ™ Gelest ™ R32- MED-Property Method ExSil 100 RG-09 2186 4014 Durometer Durometer   15% 15%15% 15% (Shore A) Elongation D412 5,000% 4,600%   850%  1330%  TensileStrength D412 8 to 9 MPa 9 to 10 MPa 6.7 MPa 4.8 MPa Tear Strength D624— 40 to 42 kN/m 22 kN/m 27 kN/m

Gelest™ ExSil 100 and Gelest™ RG-09, are commercial high-elongationsilicone elastomers, available from Gelest, Inc., (Morrisville, Pa.USA). R-32-2186 and MED-4014 are commercial high-elongation siliconeelastomers, available from NuSil Technology, LLC (Carpinteria, Calif.,USA). As discussed above, preferably the silicone elastomers haveelongations greater than 2,000%. For example, Gelest™ ExSil 100 andGelest™ RG-09 silicone elastomers having reported elongations of 5,000%and 4,600%, respectively can be used. However, it should be understoodthat other silicone elastomers having elongations less than 2,000% (forexample, R-32-2186 and MED-4014 as reported in the above Table IV) alsocan be used in accordance with this invention.

As discussed above, the silicone elastomer compositions of the presentinvention may comprise materials other than the silicone elastomers. Forexample, the silicone elastomer compositions may contain fillers,minerals and metals, dyes and pigments, antioxidants, processing aids,surfactants, plasticizers, coloring agents, and fluorescent agents.Thermoplastic and thermoset polymers also may be added to thecomposition including, for example, polyesters, polyamides, polyolefins,polyurethanes, polyureas, fluoropolymers, polystyrene, polyvinylchlorides, polycarbonates, polyethers, and polyimides Preferably, thecomposition comprises at least 50% by weight of silicone elastomer andmore preferably at least 70% by weight based on weight of composition.

Hardness of the Foamed Inner Core

Referring back to FIG. 1, a foamed inner core (4) having a geometriccenter (6) and outer skin (8) may be prepared per the molding methoddiscussed above. The outer skin (8) is generally a non-foamed regionthat forms the outer surface of the core structure. The resulting innercore preferably has a diameter within a range of about 0.100 to about1.100 inches. For example, the inner core may have a diameter within arange of about 0.250 to about 1.000 inches. In another example, theinner core may have a diameter within a range of about 0.300 to about0.800 inches. More particularly, the inner core preferably has adiameter size with a lower limit of about 0.10 or 0.12 or 0.15 or 0.25or 0.30 or 0.35 or 0.45 or 0.55 inches and an upper limit of about 0.60or 0.65 or 0.70 or 0.80 or 0.90 or 1.00 or 1.10 inches. The outer skin(8) of the inner core is relatively thin preferably having a thicknessof less than about 0.020 inches and more preferably less than 0.010inches. In one preferred embodiment, the foamed core has a “positive”hardness gradient (that is, the outer skin of the inner core is harderthan its geometric center.)

For example, the geometric center hardness of the inner core(H_(inner core center)), as measured in Shore C units, is about 10 ShoreC or greater and preferably has a lower limit of about 10 or 16 or 20 or25 or 30 or 32 or 34 or 36 or 40 Shore C and an upper limit of about 42or 44 or 48 or 50 or 52 or 56 or 60 or 62 or 65 or 68 or 70 or 74 or 78or 80 Shore C. In one preferred version, the geometric center hardnessof the inner core (H_(inner core center)) is about 60 Shore C. When aflexible, relatively soft foam is used, the (H_(inner core center)) ofthe foam may have a Shore A hardness of about 5 or greater, andpreferably has a lower limit of 5, 7, 10, 15, 20, 25, 30, or 35 Shore Aand an upper limit of about 60, 65, 70, 80, 85, or 90 Shore A. In onepreferred embodiment, the geometric center hardness of the inner core isabout 55 Shore A. The H_(inner core center), as measured in Shore Dunits, is about 15 Shore D or greater and more preferably within a rangehaving a lower limit of about 15 or 18 or 20 or 22 or 25 or 28 or 30 or32 or 36 or 40 or 44 Shore D and an upper limit of about 45 or 48 or 50or 52 or 55 or 58 or 60 or 62 or 64 or 66 or 70 or 72 or 74 or 78 or 80or 82 or 84 or 88 or 90 Shore D. Meanwhile, the outer surface hardnessof the inner core (H_(inner core surface)), as measured in Shore C, isabout 20 Shore C or greater and preferably has a lower limit of about 13or 17 or 20 or 22 or 24 or 28 or 30 or 32 or 35 or 36 or 40 or 42 or 44or 48 or 50 or 52 or 55 or 58 or 60 or 62 or 65 and an upper limit ofabout or 68 or 70 or 74 or 78 or 80 or 86 or 88 or 90 or 92 or 96 ShoreC. The outer surface hardness of the inner core((H_(inner core surface)), as measured in Shore D units, preferably hasa lower limit of about 25 or 28 or 30 or 32 or 36 or 40 or 44 Shore Dand an upper limit of about 45 or 48 or 50 or 52 or 55 or 58 or 60 or 62or 64 or 66 or 70 or 74 or 78 or 80 or 82 or 84 or 88 or 90 or 94 or 96Shore D. When measured in Shore A units, the outer surface hardness ofthe inner core ((H_(inner core surface)) general has a hardness of about5 or greater, and preferably has a lower limit of 5, 7, 10, 15, 20, 25,30, 32, 35, or 40 Shore A and an upper limit of about 50, 55, 60, 65,70, 80, 85, or 90 Shore A.

Density of the Inner Core

The foamed inner core preferably has a specific gravity of about 0.25 toabout 1.25 g/cc. That is, the density of the inner core (as measured atany point of the inner core structure) is preferably within the range ofabout 0.25 to about 1.25 g/cc. By the term, “specific gravity of theinner core” (“SG_(inner)”), it is generally meant the specific gravityof the inner core as measured at any point of the inner core structure.It should be understood, however, that the specific gravity values, astaken at different points of the inner core structure, may vary. Forexample, the foamed inner core may have a “positive” density gradient(that is, the outer surface (skin) of the inner core may have a densitygreater than the geometric center of the inner core.) In one preferredversion, the specific gravity of the geometric center of the inner core(SG_(center of inner core)) is less than 1.00 g/cc and more preferably0.90 g/cc or less. More particularly, in one version, the(SG_(center of inner core)) is in the range of about 0.10 to about 0.90g/cc. For example, the (SG_(center of inner core)) may be within a rangehaving a lower limit of about 0.10 or 0.15 of 0.20 or 0.24 or 0.30 or0.35 or 0.37 or 0.40 or 0.42 or 0.45 or 0.47 or 0.50 and an upper limitof about 0.60 or 0.65 or 0.70 or 0.74 or 0.78 or 0.80, or 0.82 or 0.84or 0.85 or 0.88 or 0.90 g/cc. Meanwhile, the specific gravity of theouter surface (skin) of the inner core (SG_(skin of inner core)), in onepreferred version, is greater than about 0.90 g/cc and more preferablygreater than 1.00 g/cc. For example, the (SG_(skin of inner core)) mayfall within the range of about 0.90 to about 2.00. More particularly, inone version, the (SG_(skin of inner core)) may have a specific gravitywith a lower limit of about 0.90 or 0.92 or 0.95 or 0.98 or 1.00 or 1.02or 1.06 or 1.10 or 1.12 or 1.15 or 1.18 and an upper limit of about 1.20or 1.24 or 1.30 or 1.32 or 1.35 or 1.38 or 1.40 or 1.44 or 1.50 or 1.60or 1.65 or 1.70 or 1.76 or 1.80 or 1.90 or 1.92 or 2.00. In otherinstances, the outer skin may have a specific gravity of less than 0.90g/cc. For example, the specific gravity of the outer skin(SG_(skin of inner core)) may be about 0.75 or 0.80 or 0.82 or 0.85 or0.88 g/cc. In such instances, wherein both the(SG_(center of inner core)) and (SG_(skin of inner core)) are less than0.90 g/cc, it is still preferred that the (SG_(center of inner core)) isless than the (SG_(skin of inner core)).

Two-Layered Cores

As discussed above, the inner core (center) is made preferably from afoamed silicone composition. Preferably, a two-layered or dual-core ismade, wherein the inner core is surrounded by an outer core layer. Inone preferred embodiment, the outer core layer is formed from anon-foamed thermoset composition and more preferably from a non-foamedthermoset rubber composition.

Suitable thermoset rubber materials that may be used to form the outercore layer include, but are not limited to, polybutadiene, polyisoprene,ethylene propylene rubber (“EPR”), ethylene-propylene-diene (“EPDM”)rubber, styrene-butadiene rubber, styrenic block copolymer rubbers (suchas “SI”, “SIS”, “SB”, “SBS”, “SIBS”, and the like, where “S” is styrene,“I” is isobutylene, and “B” is butadiene), polyalkenamers such as, forexample, polyoctenamer, butyl rubber, halobutyl rubber, polystyreneelastomers, polyethylene elastomers, polyurethane elastomers, polyureaelastomers, metallocene-catalyzed elastomers and plastomers, copolymersof isobutylene and p-alkylstyrene, halogenated copolymers of isobutyleneand p-alkylstyrene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, and blends of two or morethereof. Preferably, the outer core layer is formed from a polybutadienerubber composition.

The thermoset rubber composition may be cured using conventional curingprocesses. Suitable curing processes include, for example,peroxide-curing, sulfur-curing, high-energy radiation, and combinationsthereof. Preferably, the rubber composition contains a free-radicalinitiator selected from organic peroxides, high energy radiation sourcescapable of generating free-radicals, and combinations thereof. In onepreferred version, the rubber composition is peroxide-cured. Suitableorganic peroxides include, but are not limited to, dicumyl peroxide;n-butyl-4,4-di(t-butylperoxy) valerate;1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; and combinations thereof. In aparticular embodiment, the free radical initiator is dicumyl peroxide,including, but not limited to Perkadox® BC, commercially available fromAkzo Nobel. Peroxide free-radical initiators are generally present inthe rubber composition in an amount of at least 0.05 parts by weight per100 parts of the total rubber, or an amount within the range having alower limit of 0.05 parts or 0.1 parts or 1 part or 1.25 parts or 1.5parts or 2.5 parts or 5 parts by weight per 100 parts of the totalrubbers, and an upper limit of 2.5 parts or 3 parts or 5 parts or 6parts or 10 parts or 15 parts by weight per 100 parts of the totalrubber. Concentrations are in parts per hundred (phr) unless otherwiseindicated. As used herein, the term, “parts per hundred,” also known as“phr” or “pph” is defined as the number of parts by weight of aparticular component present in a mixture, relative to 100 parts byweight of the polymer component. Mathematically, this can be expressedas the weight of an ingredient divided by the total weight of thepolymer, multiplied by a factor of 100.

The rubber compositions may further include a reactive cross-linkingco-agent. Suitable co-agents include, but are not limited to, metalsalts of unsaturated carboxylic acids having from 3 to 8 carbon atoms;unsaturated vinyl compounds and polyfunctional monomers (e.g.,trimethylolpropane trimethacrylate); phenylene bismaleimide; andcombinations thereof. Particular examples of suitable metal saltsinclude, but are not limited to, one or more metal salts of acrylates,diacrylates, methacrylates, and dimethacrylates, wherein the metal isselected from magnesium, calcium, zinc, aluminum, lithium, and nickel.In a particular embodiment, the co-agent is selected from zinc salts ofacrylates, diacrylates, methacrylates, and dimethacrylates. In anotherparticular embodiment, the agent is zinc diacrylate (ZDA). When theco-agent is zinc diacrylate and/or zinc dimethacrylate, the co-agent istypically included in the rubber composition in an amount within therange having a lower limit of 1 or 5 or 10 or 15 or 19 or 20 parts byweight per 100 parts of the total rubber, and an upper limit of 24 or 25or 30 or 35 or 40 or 45 or 50 or 60 parts by weight per 100 parts of thebase rubber.

Radical scavengers such as a halogenated organosulfur, organicdisulfide, or inorganic disulfide compounds may be added to the rubbercomposition. These compounds also may function as “soft and fastagents.” As used herein, “soft and fast agent” means any compound or ablend thereof that is capable of making a core: 1) softer (having alower compression) at a constant “coefficient of restitution” (COR);and/or 2) faster (having a higher COR at equal compression), whencompared to a core equivalently prepared without a soft and fast agent.Preferred halogenated organosulfur compounds include, but are notlimited to, pentachlorothiophenol (PCTP) and salts of PCTP such as zincpentachlorothiophenol (ZnPCTP). Using PCTP and ZnPCTP in golf ball innercores helps produce softer and faster inner cores. The PCTP and ZnPCTPcompounds help increase the resiliency and the coefficient ofrestitution of the core. In a particular embodiment, the soft and fastagent is selected from ZnPCTP, PCTP, ditolyl disulfide, diphenyldisulfide, dixylyl disulfide, 2-nitroresorcinol, and combinationsthereof.

The rubber composition also may include filler(s) such as materialsselected from carbon black, clay and nanoclay particles as discussedabove, talc (e.g., Luzenac HAR® high aspect ratio talcs, commerciallyavailable from Luzenac America, Inc.), glass (e.g., glass flake, milledglass, and microglass), mica and mica-based pigments (e.g., Iriodin®pearl luster pigments, commercially available from The Merck Group), andcombinations thereof. Metal fillers such as, for example, particulate;powders; flakes; and fibers of copper, steel, brass, tungsten, titanium,aluminum, magnesium, molybdenum, cobalt, nickel, iron, lead, tin, zinc,barium, bismuth, bronze, silver, gold, and platinum, and alloys andcombinations thereof also may be added to the rubber composition toadjust the specific gravity of the composition as needed. As discussedfurther below, in one preferred embodiment, the specific gravity of theinner core layer (for example, foamed polyurethane) has a specificgravity less than the outer core layer (for example, polybutadienerubber). In such an event, if mineral, metal, or other fillers are addedto the polybutadiene rubber composition used to form the outer core, itis important the concentration of such fillers be sufficient so that thespecific gravity of the outer core layer is greater than the specificgravity of the inner core. For example, the concentration of the fillersmay be in an amount of at least about 5% by weight based on total weightof composition

In addition, the rubber compositions may include antioxidants to preventthe breakdown of the elastomers. Also, processing aids such as highmolecular weight organic acids and salts thereof may be added to thecomposition. Suitable organic acids are aliphatic organic acids,aromatic organic acids, saturated mono-functional organic acids,unsaturated monofunctional organic acids, multi-unsaturatedmono-functional organic acids, and dimerized derivatives thereof.Particular examples of suitable organic acids include, but are notlimited to, caproic acid, caprylic acid, capric acid, lauric acid,stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid,myristic acid, benzoic acid, palmitic acid, phenylacetic acid,naphthalenic acid, and dimerized derivatives thereof. The organic acidsare aliphatic, mono-functional (saturated, unsaturated, ormulti-unsaturated) organic acids. Salts of these organic acids may alsobe employed. The salts of organic acids include the salts of barium,lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium,strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver,aluminum, tin, or calcium, salts of fatty acids, particularly stearic,behenic, erucic, oleic, linoelic or dimerized derivatives thereof. It ispreferred that the organic acids and salts of the present invention berelatively non-migratory (they do not bloom to the surface of thepolymer under ambient temperatures) and non-volatile (they do notvolatilize at temperatures required for melt-blending.) Otheringredients such as accelerators (for example, tetra methylthiuram),processing aids, dyes and pigments, wetting agents, surfactants,plasticizers, coloring agents, fluorescent agents, chemical blowing andfoaming agents, defoaming agents, stabilizers, softening agents, impactmodifiers, antiozonants, as well as other additives known in the art maybe added to the rubber composition.

Examples of commercially-available polybutadiene rubbers that can beused in accordance with this invention, include, but are not limited to,BR 01 and BR 1220, available from BST Elastomers of Bangkok, Thailand;SE BR 1220LA and SE BR1203, available from DOW Chemical Co of Midland,Mich.; BUDENE 1207, 1207s, 1208, and 1280 available from Goodyear, Incof Akron, Ohio; BR 01, 51 and 730, available from Japan Synthetic Rubber(JSR) of Tokyo, Japan; BUNA CB 21, CB 22, CB 23, CB 24, CB 25, CB 29MES, CB 60, CB Nd 60, CB 55 NF, CB 70 B, CB KA 8967, and CB 1221,available from Lanxess Corp. of Pittsburgh. Pa.; BR1208, available fromLG Chemical of Seoul, South Korea; UBEPOL BR130B, BR150, BR150B, BR150L,BR230, BR360L, BR710, and VCR617, available from UBE Industries, Ltd. ofTokyo, Japan; EUROPRENE NEOCIS BR 60, INTENE 60 AF and P30AF, andEUROPRENE BR HV80, available from Polimeri Europa of Rome, Italy; AFDENE50 and NEODENE BR40, BR45, BR50 and BR60, available from Karbochem (PTY)Ltd. of Bruma, South Africa; KBR 01, NdBr 40, NdBR-45, NdBr 60, KBR710S, KBR 710H, and KBR 750, available from Kumho Petrochemical Co.,Ltd. Of Seoul, South Korea; DIENE 55NF, 70AC, and 320 AC, available fromFirestone Polymers of Akron, Ohio; and PBR-Nd Group II and Group III,available from Nizhnekamskneftekhim, Inc. of Nizhnekamsk, TartarstanRepublic.

The polybutadiene rubber is used in an amount of at least about 5% byweight based on total weight of composition and is generally present inan amount of about 5% to about 100%, or an amount within a range havinga lower limit of 5% or 10% or 20% or 30% or 40% or 50% and an upperlimit of 55% or 60% or 70% or 80% or 90% or 95% or 100%. Preferably, theconcentration of polybutadiene rubber is about 40 to about 95 weightpercent. If desirable, lesser amounts of other thermoset materials maybe incorporated into the base rubber. Such materials include the rubbersdiscussed above, for example, cis-polyisoprene, trans-polyisoprene,balata, polychloroprene, polynorbornene, polyoctenamer, polypentenamer,butyl rubber, EPR, EPDM, styrene-butadiene, and the like.

In alternative embodiments, the outer core layer may comprise athermoplastic material, for example, an ionomer composition containingacid groups that are at least partially-neutralized. Suitable ionomercompositions include partially-neutralized ionomers andhighly-neutralized ionomers (HNPs), including ionomers formed fromblends of two or more partially-neutralized ionomers, blends of two ormore highly-neutralized ionomers, and blends of one or morepartially-neutralized ionomers with one or more highly-neutralizedionomers. For purposes of the present disclosure, “HNP” refers to anacid copolymer after at least 70% of all acid groups present in thecomposition are neutralized. Preferred ionomers are salts of O/X- andO/X/Y-type acid copolymers, wherein O is an α-olefin, X is a C₃-C₈α,β-ethylenically unsaturated carboxylic acid, and Y is a softeningmonomer. O is preferably selected from ethylene and propylene. X ispreferably selected from methacrylic acid, acrylic acid, ethacrylicacid, crotonic acid, and itaconic acid. Methacrylic acid and acrylicacid are particularly preferred. Y is preferably selected from (meth)acrylate and alkyl (meth) acrylates wherein the alkyl groups have from 1to 8 carbon atoms, including, but not limited to, n-butyl (meth)acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl(meth) acrylate.

Preferred O/X and O/X/Y-type copolymers include, without limitation,ethylene acid copolymers, such as ethylene/(meth)acrylic acid,ethylene/(meth)acrylic acid/maleic anhydride, ethylene/(meth)acrylicacid/maleic acid mono-ester, ethylene/maleic acid, ethylene/maleic acidmono-ester, ethylene/(meth)acrylic acid/n-butyl (meth)acrylate,ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate,ethylene/(meth)acrylic acid/methyl (meth)acrylate,ethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers, and thelike. The term, “copolymer,” as used herein, includes polymers havingtwo types of monomers, those having three types of monomers, and thosehaving more than three types of monomers. Preferred α, β-ethylenicallyunsaturated mono- or dicarboxylic acids are (meth) acrylic acid,ethacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconicacid. (Meth) acrylic acid is most preferred. As used herein, “(meth)acrylic acid” means methacrylic acid and/or acrylic acid. Likewise,“(meth) acrylate” means methacrylate and/or acrylate.

In a particularly preferred version, highly neutralized E/X- andE/X/Y-type acid copolymers, wherein E is ethylene, X is a C₃-C₈α,β-ethylenically unsaturated carboxylic acid, and Y is a softeningmonomer are used. X is preferably selected from methacrylic acid,acrylic acid, ethacrylic acid, crotonic acid, and itaconic acid.Methacrylic acid and acrylic acid are particularly preferred. Y ispreferably an acrylate selected from alkyl acrylates and aryl acrylatesand preferably selected from (meth) acrylate and alkyl (meth) acrylateswherein the alkyl groups have from 1 to 8 carbon atoms, including, butnot limited to, n-butyl (meth) acrylate, isobutyl (meth) acrylate,methyl (meth) acrylate, and ethyl (meth) acrylate. Preferred E/X/Y-typecopolymers are those wherein X is (meth) acrylic acid and/or Y isselected from (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. Morepreferred E/X/Y-type copolymers are ethylene/(meth) acrylic acid/n-butylacrylate, ethylene/(meth) acrylic acid/methyl acrylate, andethylene/(meth) acrylic acid/ethyl acrylate.

The amount of ethylene in the acid copolymer is typically at least 15wt. %, preferably at least 25 wt. %, more preferably least 40 wt. %, andeven more preferably at least 60 wt. %, based on total weight of thecopolymer. The amount of C₃ to C₈ α, β-ethylenically unsaturated mono-or dicarboxylic acid in the acid copolymer is typically from 1 wt. % to35 wt. %, preferably from 5 wt. % to 30 wt. %, more preferably from 5wt. % to 25 wt. %, and even more preferably from 10 wt. % to 20 wt. %,based on total weight of the copolymer. The amount of optional softeningcomonomer in the acid copolymer is typically from 0 wt. % to 50 wt. %,preferably from 5 wt. % to 40 wt. %, more preferably from 10 wt. % to 35wt. %, and even more preferably from 20 wt. % to 30 wt. %, based ontotal weight of the copolymer. “Low acid” and “high acid” ionomericpolymers, as well as blends of such ionomers, may be used. In general,low acid ionomers are considered to be those containing 16 wt. % or lessof acid moieties, whereas high acid ionomers are considered to be thosecontaining greater than 16 wt. % of acid moieties.

The various O/X, E/X, O/X/Y, and E/X/Y-type copolymers are at leastpartially neutralized with a cation source, optionally in the presenceof a high molecular weight organic acid, such as those disclosed in U.S.Pat. No. 6,756,436, the entire disclosure of which is herebyincorporated herein by reference. The acid copolymer can be reacted withthe optional high molecular weight organic acid and the cation sourcesimultaneously, or prior to the addition of the cation source. Suitablecation sources include, but are not limited to, metal ion sources, suchas compounds of alkali metals, alkaline earth metals, transition metals,and rare earth elements; ammonium salts and monoamine salts; andcombinations thereof. Preferred cation sources are compounds ofmagnesium, sodium, potassium, cesium, calcium, barium, manganese,copper, zinc, lead, tin, aluminum, nickel, chromium, lithium, and rareearth metals.

Other suitable thermoplastic polymers that may be used to form the outercore layer include, but are not limited to, the following polymers(including homopolymers, copolymers, and derivatives thereof.)

(a) polyesters, particularly those modified with a compatibilizing groupsuch as sulfonate or phosphonate, including modified poly(ethyleneterephthalate), modified poly(butylene terephthalate), modifiedpoly(propylene terephthalate), modified poly(trimethyleneterephthalate), modified poly(ethylene naphthenate), and those disclosedin U.S. Pat. Nos. 6,353,050, 6,274,298, and 6,001,930, the entiredisclosures of which are hereby incorporated herein by reference, andblends of two or more thereof;

(b) polyamides, polyamide-ethers, and polyamide-esters, and thosedisclosed in U.S. Pat. Nos. 6,187,864, 6,001,930, and 5,981,654, theentire disclosures of which are hereby incorporated herein by reference,and blends of two or more thereof;

(c) polyurethanes, polyureas, polyurethane-polyurea hybrids, and blendsof two or more thereof;

(d) fluoropolymers, such as those disclosed in U.S. Pat. Nos. 5,691,066,6,747,110 and 7,009,002, the entire disclosures of which are herebyincorporated herein by reference, and blends of two or more thereof;

(e) polystyrenes, such as poly(styrene-co-maleic anhydride),acrylonitrile-butadiene-styrene, poly(styrene sulfonate), polyethylenestyrene, and blends of two or more thereof;

(f) polyvinyl chlorides and grafted polyvinyl chlorides, and blends oftwo or more thereof;

(g) polycarbonates, blends ofpolycarbonate/acrylonitrile-butadiene-styrene, blends ofpolycarbonate/polyurethane, blends of polycarbonate/polyester, andblends of two or more thereof;

(h) polyethers, such as polyarylene ethers, polyphenylene oxides, blockcopolymers of alkenyl aromatics with vinyl aromatics and polyamicesters,and blends of two or more thereof;

(i) polyimides, polyetherketones, polyamideimides, and blends of two ormore thereof; and

(j) polycarbonate/polyester copolymers and blends.

It also is recognized that thermoplastic materials can be “converted”into thermoset materials by cross-linking the polymer chains so theyform a network structure, and such cross-linked thermoplastic materialsmay be used to form the core layers in accordance with this invention.For example, thermoplastic polyolefins such as linear low densitypolyethylene (LLDPE), low density polyethylene (LDPE), and high densitypolyethylene (HDPE) may be cross-linked to form bonds between thepolymer chains. The cross-linked thermoplastic material typically hasimproved physical properties and strength over non-cross-linkedthermoplastics, particularly at temperatures above the crystallinemelting point. Preferably a partially or fully-neutralized ionomer, asdescribed above, is covalently cross-linked to render it into athermoset composition (that is, it contains at least some level ofcovalent, irreversable cross-links). Thermoplastic polyurethanes andpolyureas also may be converted into thermoset materials in accordancewith the present invention.

The cross-linked thermoplastic material may be created by exposing thethermoplastic to: 1) a high-energy radiation treatment, such as electronbeam or gamma radiation, such as disclosed in U.S. Pat. No. 5,891,973,which is incorporated by reference herein, 2) lower energy radiation,such as ultra-violet (UV) or infra-red (IR) radiation; 3) a solutiontreatment, such as an isocyanate or a silane; 4) incorporation ofadditional free radical initiator groups in the thermoplastic prior tomolding; and/or 5) chemical modification, such as esterification orsaponification, to name a few.

Modifications in thermoplastic polymeric structure of thermoplastic canbe induced by a number of methods, including exposing the thermoplasticmaterial to high-energy radiation or through a chemical process usingperoxide. Radiation sources include, but are not limited to, gamma-rays,electrons, neutrons, protons, x-rays, helium nuclei, or the like. Gammaradiation, typically using radioactive cobalt atoms and allows forconsiderable depth of treatment, if necessary. For core layers requiringlower depth of penetration, electron-beam accelerators or UV and IRlight sources can be used. Useful UV and IR irradiation methods aredisclosed in U.S. Pat. Nos. 6,855,070 and 7,198,576, which areincorporated herein by reference. The thermoplastic core layers may beirradiated at dosages greater than 0.05 Mrd, preferably ranging from 1Mrd to 20 Mrd, more preferably from 2 Mrd to 15 Mrd, and most preferablyfrom 4 Mrd to 10 Mrd. In one preferred embodiment, the cores areirradiated at a dosage from 5 Mrd to 8 Mrd and in another preferredembodiment, the cores are irradiated with a dosage from 0.05 Mrd to 3Mrd, more preferably 0.05 Mrd to 1.5 Mrd.

For example, a core assembly having a thermoplastic layer may beconverted to a thermoset layer by placing the core assembly on a slowlymove along a channel. Radiation from a radiation source, such as gammarays, is allowed to contact the surface of the cores. The source ispositioned to provide a generally uniform dose of radiation to the coresas they roll along the channel. The speed of the cores as they passthrough the radiation source is easily controlled to ensure the coresreceive sufficient dosage to create the desired hardness gradient. Thecores are irradiated with a dosage of 1 or more Mrd, more preferably 2Mrd to 15 Mrd. The intensity of the dosage is typically in the range of1 MeV to 20 MeV. For thermoplastic resins having a reactive group (e.g.,ionomers, thermoplastic urethanes, and the like), treating thethermoplastic core layer in a chemical solution of an isocyanate or anamine affects cross-linking and provides a harder surface and subsequenthardness gradient. Incorporation of peroxide or other free-radicalinitiator in the thermoplastic polymer, prior to molding or forming,also allows for heat curing on the molded core layer to create thedesired hardness gradient. By proper selection of time/temperature, anannealing process can be used to create a gradient. Suitable annealingand/or peroxide (free radical) methods are such as disclosed in U.S.Pat. Nos. 5,274,041 and 5,356,941, respectively, which are incorporatedby reference herein. Additionally, silane or amino-silane crosslinkingmay also be employed as disclosed in U.S. Pat. No. 7,279,529, thedisclosure of which incorporated herein by reference. The core layer maybe chemically treated in a solution, such as a solution containing oneor more isocyanates, to form the desired “positive hardness gradient.”The cores are typically exposed to the solution containing theisocyanate by immersing them in a bath at a particular temperature for agiven time. Exposure time should be greater than 1 minute, preferablyfrom 1 minute to 120 minutes, more preferably 5 minutes to 90 minutes,and most preferably 10 minutes to 60 minutes. In one preferredembodiment, the cores are immersed in the treating solution from 15minutes to 45 minutes, more preferably from 20 minutes to 40 minutes,and most preferably from 25 minutes to 30 minutes.

The core layers may be chemically treated in a solution, such as asolution containing one or more isocyanates, to form the desired“positive hardness gradient.” The cores are typically exposed to thesolution containing the isocyanate by immersing them in a bath at aparticular temperature for a given time. Exposure time should be greaterthan 1 minute, preferably from 1 minute to 120 minutes, more preferably5 minutes to 90 minutes, and most preferably 10 minutes to 60 minutes.In one preferred embodiment, the cores are immersed in the treatingsolution from 15 minutes to 45 minutes, more preferably from 20 minutesto 40 minutes, and most preferably from 25 minutes to 30 minutes. Bothirradiative and chemical methods promote molecular bonding, orcross-links, within the TP polymer. Radiative methods permitcross-linking and grafting in situ on finished products andcross-linking occurs at lower temperatures with radiation than withchemical processing. Chemical methods depend on the particular polymer,the presence of modifying agents, and variables in processing, such asthe level of irradiation. Significant property benefits in thethermoplastic materials can be attained and include, but are not limitedto, improved thermomechanical properties; lower permeability andimproved chemical resistance; reduced stress cracking; and overallimprovement in physical toughness.

Additional embodiments involve the use of plasticizers to treat the corelayers, thereby creating a softer outer portion of the core for a“negative” hardness gradient. The plasticizer may be reactive (such ashigher alkyl acrylates) or non-reactive (that is, phthalates,dioctylphthalate, or stearamides, etc). Other suitable plasticizersinclude, but are not limited to, oxa acids, fatty amines, fatty amides,fatty acid esters, phthalates, adipates, and sebacates. Oxa acids arepreferred plasticizers, more preferably those having at least one or twoacid functional groups and a variety of different chain lengths.Preferred oxa acids include 3,6-dioxaheptanoic acid,3,6,9-trioxadecanoic acid, diglycolic acid, 3,6,9-trioxaundecanoic acid,polyglycol diacid, and 3,6-dioxaoctanedioic acid, such as thosecommercially available from Archimica of Wilmington, Del. Any means ofchemical degradation will also result in a “negative” hardness gradient.Chemical modifications such as esterification or saponification are alsosuitable for modification of the thermoplastic core layer surface andcan result in the desired “positive hardness gradient.

Core Structure

As discussed above, the core of the golf ball of this inventionpreferably has a dual-layered structure comprising an inner core andouter core layer. Referring to FIG. 3, one version of a golf ball thatcan be made in accordance with this invention is generally indicated at(20). The ball (20) contains a dual-layered core (22) having an innercore (center) (22 a) and outer core layer (22 b) surrounded by asingle-layered cover (24). The inner core (22 a) is relatively small involume and generally has a diameter within a range of about 0.10 toabout 1.10 inches. More particularly, the inner core (22 a) preferablyhas a diameter size with a lower limit of about 0.15 or 0.25 or 0.35 or0.45 or 0.55 inches and an upper limit of about 0.60 or 0.70 or 0.80 or0.90 inches. In one preferred version, the diameter of the inner core(22 a) is in the range of about 0.025 to about 0.080 inches, morepreferably about 0.030 to about 0.075 inches. Meanwhile, the outer corelayer (22 b) generally has a thickness within a range of about 0.010 toabout 0.250 inches and preferably has a lower limit of 0.010 or 0.020 or0.025 or 0.030 inches and an upper limit of 0.070 or 0.080 or 0.100 or0.200 inches. In one preferred version, the outer core layer has athickness in the range of about 0.040 to about 0.170 inches, morepreferably about 0.060 to about 0.150 inches.

Referring to FIG. 4, in another version, the golf ball (25) contains adual-core (26) having an inner core (center) (26 a) and outer core layer(26 b). The dual-core (26) is surrounded by a multi-layered cover (28)having an inner cover layer (28 a) and outer cover layer (28 b).

The hardness of the core sub-assembly (inner core and outer core layer)is an important property. In general, cores with relatively highhardness values have higher compression and tend to have good durabilityand resiliency. However, some high compression balls are stiff and thismay have a detrimental effect on shot control and placement. Thus, theoptimum balance of hardness in the core sub-assembly needs to beattained.

In one preferred golf ball, the inner core (center) has a “positive”hardness gradient (that is, the outer surface of the inner core isharder than its geometric center); and the outer core layer has a“positive” hardness gradient (that is, the outer surface of the outercore layer is harder than the inner surface of the outer core layer.) Insuch cases where both the inner core and outer core layer each has a“positive” hardness gradient, the outer surface hardness of the outercore layer is preferably greater than the hardness of the geometriccenter of the inner core. In one preferred version, the positivehardness gradient of the inner core is in the range of about 2 to about40 Shore C units and even more preferably about 10 to about 25 Shore Cunits; while the positive hardness gradient of the outer core is in therange of about 2 to about 20 Shore C and even more preferably about 3 toabout 10 Shore C.

In an alternative version, the inner core may have a positive hardnessgradient; and the outer core layer may have a “zero” hardness gradient(that is, the hardness values of the outer surface of the outer corelayer and the inner surface of the outer core layer are substantiallythe same) or a “negative” hardness gradient (that is, the outer surfaceof the outer core layer is softer than the inner surface of the outercore layer.) For example, in one version, the inner core has a positivehardness gradient; and the outer core layer has a negative hardnessgradient in the range of about 2 to about 25 Shore C. In a secondalternative version, the inner core may have a zero or negative hardnessgradient; and the outer core layer may have a positive hardnessgradient. Still yet, in another embodiment, both the inner core andouter core layers have zero or negative hardness gradients.

In general, hardness gradients are further described in Bulpett et al.,U.S. Pat. Nos. 7,537,529 and 7,410,429, the disclosures of which arehereby incorporated by reference. Methods for measuring the hardness ofthe inner core and outer core layers along with other layers in the golfball and determining the hardness gradients of the various layers aredescribed in further detail below. The core layers have positive,negative, or zero hardness gradients defined by hardness measurementsmade at the outer surface of the inner core (or outer surface of theouter core layer) and radially inward towards the center of the innercore (or inner surface of the outer core layer). These measurements aremade typically at 2-mm increments as described in the test methodsbelow. In general, the hardness gradient is determined by subtractingthe hardness value at the innermost portion of the component beingmeasured (for example, the center of the inner core or inner surface ofthe outer core layer) from the hardness value at the outer surface ofthe component being measured (for example, the outer surface of theinner core or outer surface of the outer core layer).

Positive Hardness Gradient.

For example, if the hardness value of the outer surface of the innercore is greater than the hardness value of the inner core's geometriccenter (that is, the inner core has a surface harder than its geometriccenter), the hardness gradient will be deemed “positive” (a largernumber minus a smaller number equals a positive number.) For example, ifthe outer surface of the inner core has a hardness of 67 Shore C and thegeometric center of the inner core has a hardness of 60 Shore C, thenthe inner core has a positive hardness gradient of 7. Likewise, if theouter surface of the outer core layer has a greater hardness value thanthe inner surface of the outer core layer, the given outer core layerwill be considered to have a positive hardness gradient.

Negative Hardness Gradient.

On the other hand, if the hardness value of the outer surface of theinner core is less than the hardness value of the inner core's geometriccenter (that is, the inner core has a surface softer than its geometriccenter), the hardness gradient will be deemed “negative.” For example,if the outer surface of the inner core has a hardness of 68 Shore C andthe geometric center of the inner core has a hardness of 70 Shore C,then the inner core has a negative hardness gradient of 2. Likewise, ifthe outer surface of the outer core layer has a lesser hardness valuethan the inner surface of the outer core layer, the given outer corelayer will be considered to have a negative hardness gradient.

Zero Hardness Gradient.

In another example, if the hardness value of the outer surface of theinner core is substantially the same as the hardness value of the innercore's geometric center (that is, the surface of the inner core hasabout the same hardness as the geometric center), the hardness gradientwill be deemed “zero.” For example, if the outer surface of the innercore and the geometric center of the inner core each has a hardness of65 Shore C, then the inner core has a zero hardness gradient. Likewise,if the outer surface of the outer core layer has a hardness valueapproximately the same as the inner surface of the outer core layer, theouter core layer will be considered to have a zero hardness gradient.

More particularly, the term, “positive hardness gradient” as used hereinmeans a hardness gradient of positive 3 Shore C or greater, preferably 7Shore C or greater, more preferably 10 Shore C, and even more preferably20 Shore C or greater. The term, “zero hardness gradient” as used hereinmeans a hardness gradient of less than 3 Shore C, preferably less than 1Shore C and may have a value of zero or negative 1 to negative 10 ShoreC. The term, “negative hardness gradient” as used herein means ahardness value of less than zero, for example, negative 3, negative 5,negative 7, negative 10, negative 15, or negative 20 or negative 25. Theterms, “zero hardness gradient” and “negative hardness gradient” may beused herein interchangeably to refer to hardness gradients of negative 1to negative 10.

The inner core preferably has a geometric center hardness(H_(inner core center)) of about 5 Shore D or greater. For example, the(H_(inner core center)) may be in the range of about 5 to about 88 ShoreD and more particularly within a range having a lower limit of about 5or 10 or 18 or 20 or 26 or 30 or 34 or 36 or 38 or 42 or 48 or 50 or 52Shore D and an upper limit of about 54 or 56 or 58 or 60 or 62 or 64 or68 or 70 or 74 or 76 or 80 or 82 or 84 or 88 Shore D. In anotherexample, the center hardness of the inner core (H_(inner core center)),as measured in Shore C units, is preferably about 10 Shore C or greater;for example, the H_(inner core center) may have a lower limit of about10 or 14 or 16 or 20 or 23 or 24 or 28 or 31 or 34 or 37 or 40 or 44Shore C and an upper limit of about 46 or 48 or 50 or 51 or 53 or 55 or58 or 61 or 62 or 65 or 68 or 71 or 74 or 76 or 78 or 79 or 80 or 84 or90 Shore C. Concerning the outer surface hardness of the inner core(H_(inner core surface)), this hardness is preferably about 12 Shore Dor greater; for example, the H_(inner core surface) may fall within arange having a lower limit of about 12 or 15 or 18 or 20 or 22 or 26 or30 or 34 or 36 or 38 or 42 or 48 or 50 or 52 Shore D and an upper limitof about 54 or 56 or 58 or 60 or 62 or 70 or 72 or 75 or 78 or 80 or 82or 84 or 86 or 90 Shore D. In one version, the outer surface hardness ofthe inner core (H_(inner core surface)), as measured in Shore C units,has a lower limit of about 13 or 15 or 18 or 20 or 22 or 24 or 27 or 28or 30 or 32 or 34 or 38 or 44 or 47 or 48 Shore C and an upper limit ofabout 50 or 54 or 56 or 61 or 65 or 66 or 68 or 70 or 73 or 76 or 78 or80 or 84 or 86 or 88 or 90 or 92 Shore C. In another version, thegeometric center hardness (H_(inner core center)) is in the range ofabout 10 Shore C to about 50 Shore C; and the outer surface hardness ofthe inner core (H_(inner core surface)) is in the range of about 5 ShoreC to about 50 Shore C.

On the other hand, the outer core layer preferably has an outer surfacehardness (H_(outer surface of OC)) of about 40 Shore D or greater, andmore preferably within a range having a lower limit of about 40 or 42 or44 or 46 or 48 or 50 or 52 and an upper limit of about 54 or 56 or 58 or60 or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90Shore D. The outer surface hardness of the outer core layer(H_(outer surface of OC)), as measured in Shore C units, preferably hasa lower limit of about 40 or 42 or 45 or 48 or 50 or 54 or 58 or 60 or63 or 65 or 67 or 70 or 72 or 73 or 76 Shore C, and an upper limit ofabout 78 or 80 or 84 or 87 or 88 or 89 or 90 or 92 or 95 Shore C. And,the inner surface of the outer core layer (H_(inner surface of OC))preferably has a hardness of about 40 Shore D or greater, and morepreferably within a range having a lower limit of about 40 or 42 or 44or 46 or 48 or 50 or 52 and an upper limit of about 54 or 56 or 58 or 60or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90 ShoreD. The inner surface hardness of the outer core layer(H_(inner surface of OC)), as measured in Shore C units, preferably hasa lower limit of about 40 or 42 or 44 or 45 or 47 or 50 or 52 or 54 or55 or 58 or 60 or 63 or 65 or 67 or 70 or 73 or 76 Shore C, and an upperlimit of about 78 or 80 or 85 or 88 or 89 or 90 or 92 or 95 Shore C.When measured in Shore A units, the outer surface hardness of the outercore ((H_(outer surface of OC)) generally has a hardness of about 5 orgreater, and preferably has a lower limit of 5, 7, 10, 15, 20, 25, 30,35, 40, or 42 Shore A and an upper limit of about 50, 55, 60, 65, 70,80, 85, or 90 Shore A.

In one embodiment, the outer surface hardness of the outer core layer(H_(outer surface of OC)), is less than the outer surface hardness(H_(inner core surface)) of the inner core by at least 3 Shore C unitsand more preferably by at least 5 Shore C.

In a second embodiment, the outer surface hardness of the outer corelayer (H_(outer surface of OC)), is greater than the outer surfacehardness (H_(inner core surface)) of the inner core by at least 3 ShoreC units and more preferably by at least 5 Shore C.

As discussed above, the inner core is preferably formed from a foamedthermoplastic or thermoset composition and more preferably foamedpolyurethanes. And, the outer core layer is formed preferably from anon-foamed thermoset composition such as polybutadiene rubber.

The core structure also has a hardness gradient across the entire coreassembly. In one embodiment, the (H_(inner core center)) is in the rangeof about 10 Shore C to about 60 Shore C, preferably about 13 Shore C toabout 55 Shore C; and the (H_(outer surface of OC)) is in the range ofabout 65 to about 96 Shore C, preferably about 68 Shore C to about 94Shore C or about 75 Shore C to about 93 Shore C, to provide a positivehardness gradient across the core assembly. The gradient across the coreassembly will vary based on several factors including, but not limitedto, the dimensions of the inner core, intermediate core, and outer corelayers.

The inner core preferably has a diameter in the range of about 0.100 toabout 1.100 inches. For example, the inner core may have a diameterwithin a range of about 0.100 to about 0.500 inches. In another example,the inner core may have a diameter within a range of about 0.300 toabout 0.800 inches. More particularly, the inner core may have adiameter size with a lower limit of about 0.10 or 0.12 or 0.15 or 0.25or 0.30 or 0.35 or 0.45 or 0.55 inches and an upper limit of about 0.60or 0.65 or 0.70 or 0.80 or 0.90 or 1.00 or 1.10 inches. As far as theouter core layer is concerned, it preferably has a thickness in therange of about 0.100 to about 0.750 inches. For example, the lower limitof thickness may be about 0.050 or 0.100 or 0.150 or 0.200 or 0.250 or0.300 or 0.340 or 0.400 and the upper limit may be about 0.500 or 0.550or 0.600 or 0.650 or 0.700 or 0.750 inches.

Dual-layered core structures containing layers with various thicknessand volume levels may be made in accordance with this invention. Forexample, in one version, the total diameter of the core structure is0.20 inches and the total volume of the core structure is 0.23 cc. Moreparticularly, in this example, the diameter of the inner core is 0.10inches and the volume of the inner core is 0.10 cc; while the thicknessof the outer core is 0.100 inches and the volume of the outer core is0.13 cc. In another version, the total core diameter is about 1.55inches and the total core volume is 31.96 cc. In this version, the outercore layer has a thickness of 0.400 inches and volume of 28.34 cc.Meanwhile, the inner core has a diameter of 0.75 inches and volume of3.62 cm. In one embodiment, the volume of the outer core layer isgreater than the volume of the inner core. In another embodiment, thevolume of the outer core layer and inner core are equivalent. In stillanother embodiment, the volume of the outer core layer is less than thevolume of the inner core. Other examples of core structures containinglayers of varying thicknesses and volumes are described below in TableA.

TABLE A Sample Core Dimensions Thermoset Foamed Total Core Total CoreOuter Core Outer Core Inner Core Volume of Example Diameter VolumeThickness Volume Diameter Inner Core A 0.30″ 0.23 cc 0.100″ 0.13 cc0.10″ 0.10 cc B 1.60″ 33.15 cc 0.750″ 33.05 cc 0.10″ 0.10 cc C 1.55″31.96 cc 0.225″ 11.42 cc 1.10″ 11.42 cc D 1.55″ 31.96 cc 0.400″ 28.34 cc0.75″ 3.62 cc E 1.55″ 31.96 cc 0.525″ 28.34 cc 0.50″ 3.62 cc

In one preferred embodiment, the inner core has a specific gravity inthe range of about 0.25 to about 1.25 g/cc. Also, as discussed above,the specific gravity of the inner core may vary at different points ofthe inner core structure. That is, there may be a specific gravitygradient in the inner core. For example, in one preferred version, thegeometric center of the inner core has a density in the range of about0.25 to about 0.75 g/cc; while the outer skin of the inner core has adensity in the range of about 0.75 to about 1.50 g/cc.

Meanwhile, the outer core layer preferably has a relatively highspecific gravity. Thus, the specific gravity of the inner core layer(SG_(inner)) is preferably less than the specific gravity of the outercore layer (SG_(outer)). By the term, “specific gravity of the outercore layer” (“SG_(outer)”), it is generally meant the specific gravityof the outer core layer as measured at any point of the outer corelayer. The specific gravity values at different points in the outer corelayer may vary. That is, there may be specific gravity gradients in theouter core layer similar to the inner core. For example, the outer corelayer may have a specific gravity within a range having a lower limit ofabout 0.50 or 0.60 or 0.70 or 0.75 or 0.85 or 0.95 or 1.00 or 1.10 or1.25 or 1.30 or 1.36 or 1.40 or 1.42 or 1.48 or 1.50 or 1.60 or 1.66 or1.75 or 2.00 and an upper limit of 2.50 or 2.60 or 2.80 or 2.90 or 3.00or 3.10 or 3.25 or 3.50 or 3.60 or 3.80 or 4.00, 4.25 or 5.00 or 5.10 or5.20 or 5.30 or 5.40 or 6.00 or 6.20 or 6.25 or 6.30 or 6.40 or 6.50 or7.00 or 7.10 or 7.25 or 7.50 or 7.60 or 7.65 or 7.80 or 8.00 or 8.20 or8.50 or 9.00 or 9.75 or 10.00 g/cc.

In general, the specific gravities of the respective pieces of an objectaffect the Moment of Inertia (MOI) of the object. The Moment of Inertiaof a ball (or other object) about a given axis generally refers to howdifficult it is to change the ball's angular motion about that axis. Ifthe ball's mass is concentrated towards the center (the center piece(for example, inner core) has a higher specific gravity than the outerpiece (for example, outer core layers), less force is required to changeits rotational rate, and the ball has a relatively low Moment ofInertia. In such balls, most of the mass is located close to the ball'saxis of rotation and less force is needed to generate spin. Thus, theball has a generally high spin rate as the ball leaves the club's faceafter making impact. Conversely, if the ball's mass is concentratedtowards the outer surface (the outer piece (for example, outer corelayers) has a higher specific gravity than the center piece (forexample, inner core), more force is required to change its rotationalrate, and the ball has a relatively high Moment of Inertia. That is, insuch balls, most of the mass is located away from the ball's axis ofrotation and more force is needed to generate spin. Such balls have agenerally low spin rate as the ball leaves the club's face after makingimpact.

More particularly, as described in Sullivan, U.S. Pat. No. 6,494,795 andLadd et al., U.S. Pat. No. 7,651,415, the formula for the Moment ofInertia for a sphere through any diameter is given in the CRC StandardMathematical Tables, 24th Edition, 1976 at 20 (hereinafter CRCreference). The term, “specific gravity” as used herein, has itsordinary and customary meaning, that is, the ratio of the density of asubstance to the density of water at 4° C., and the density of water atthis temperature is 1 g/cm³.

In one embodiment, the golf balls of this invention are relatively lowspin and long distance. That is, the foam core construction, asdescribed above, wherein the inner core is made of a foamed compositionhelps provide a relatively low spin ball having good resiliency. Theinner foam cores of this invention preferably have a Coefficient ofRestitution (COR) of about 0.300 or greater; more preferably about 0.400or greater, and even more preferably about 0.450 or greater. Theresulting balls containing the dual-layered core constructions of thisinvention and cover of at least one layer preferably have a COR of about0.700 or greater, more preferably about 0.730 or greater; and even morepreferably about 0.750 to 0.810 or greater. The inner foam corespreferably have a Soft Center Deflection Index (“SCDI”) compression, asdescribed in the Test Methods below, in the range of about 50 to about190, and more preferably in the range of about 60 to about 170.

The USGA has established a maximum weight of 45.93 g (1.62 ounces) forgolf balls. For play outside of USGA rules, the golf balls can beheavier. In one preferred embodiment, the weight of the multi-layeredcore is in the range of about 28 to about 38 grams. Also, golf ballsmade in accordance with this invention can be of any size, although theUSGA requires that golf balls used in competition have a diameter of atleast 1.68 inches. For play outside of United States Golf Association(USGA) rules, the golf balls can be of a smaller size. Normally, golfballs are manufactured in accordance with USGA requirements and have adiameter in the range of about 1.68 to about 1.80 inches. As discussedfurther below, the golf ball contains a cover which may be multi-layeredand in addition may contain intermediate (casing) layers, and thethickness levels of these layers also must be considered. Thus, ingeneral, the dual-layer core structure normally has an overall diameterwithin a range having a lower limit of about 1.00 or 1.20 or 1.30 or1.40 inches and an upper limit of about 1.58 or 1.60 or 1.62 or 1.66inches, and more preferably in the range of about 1.3 to 1.65 inches. Inone embodiment, the diameter of the core sub-assembly is in the range ofabout 1.45 to about 1.62 inches.

Cover Structure

The golf ball sub-assemblies of this invention may be enclosed with oneor more cover layers. The golf ball sub-assembly may comprise themulti-layered core structure as discussed above. In other versions, thegolf ball sub-assembly includes the core structure and one or morecasing (mantle) layers disposed about the core. In one particularlypreferred version, the golf ball includes a multi-layered covercomprising inner and outer cover layers. The inner cover layer ispreferably formed from a composition comprising an ionomer or a blend oftwo or more ionomers that helps impart hardness to the ball. In aparticular embodiment, the inner cover layer is formed from acomposition comprising a high acid ionomer. A particularly suitable highacid ionomer is Surlyn 8150® (DuPont). Surlyn 8150® is a copolymer ofethylene and methacrylic acid, having an acid content of 19 wt %, whichis 45% neutralized with sodium. In another particular embodiment, theinner cover layer is formed from a composition comprising a high acidionomer and a maleic anhydride-grafted non-ionomeric polymer. Aparticularly suitable maleic anhydride-grafted polymer is Fusabond 525D®(DuPont). Fusabond 525D® is a maleic anhydride-grafted,metallocene-catalyzed ethylene-butene copolymer having about 0.9 wt %maleic anhydride grafted onto the copolymer. A particularly preferredblend of high acid ionomer and maleic anhydride-grafted polymer is an 84wt %/16 wt % blend of Surlyn 8150® and Fusabond 525D®. Blends of highacid ionomers with maleic anhydride-grafted polymers are furtherdisclosed, for example, in U.S. Pat. Nos. 6,992,135 and 6,677,401, theentire disclosures of which are hereby incorporated herein by reference.

The inner cover layer also may be formed from a composition comprising a50/45/5 blend of Surlyn® 8940/Surlyn® 9650/Nucrel® 960, and, in aparticularly preferred embodiment, the composition has a materialhardness of from 80 to 85 Shore C. In yet another version, the innercover layer is formed from a composition comprising a 50/25/25 blend ofSurlyn® 8940/Surlyn® 9650/Surlyn® 9910, preferably having a materialhardness of about 90 Shore C. The inner cover layer also may be formedfrom a composition comprising a 50/50 blend of Surlyn® 8940/Surlyn®9650, preferably having a material hardness of about 86 Shore C. Acomposition comprising a 50/50 blend of Surlyn® 8940 and Surlyn® 7940also may be used. Surlyn® 8940 is an E/MAA copolymer in which the MAAacid groups have been partially neutralized with sodium ions. Surlyn®9650 and Surlyn® 9910 are two different grades of E/MAA copolymer inwhich the MAA acid groups have been partially neutralized with zincions. Nucrel® 960 is an E/MAA copolymer resin nominally made with 15 wt% methacrylic acid.

A wide variety of materials may be used for forming the outer coverincluding, for example, polyurethanes; polyureas; copolymers, blends andhybrids of polyurethane and polyurea; olefin-based copolymer ionomerresins (for example, Surlyn® ionomer resins and DuPont HPF® 1000 andHPF® 2000, commercially available from DuPont; Iotek® ionomers,commercially available from ExxonMobil Chemical Company; Amplify® 10ionomers of ethylene acrylic acid copolymers, commercially availablefrom The Dow Chemical Company; and Clarix® ionomer resins, commerciallyavailable from A. Schulman Inc.); polyethylene, including, for example,low density polyethylene, linear low density polyethylene, and highdensity polyethylene; polypropylene; rubber-toughened olefin polymers;acid copolymers, for example, poly(meth)acrylic acid, which do notbecome part of an ionomeric copolymer; plastomers; flexomers;styrene/butadiene/styrene block copolymers;styrene/ethylene-butylene/styrene block copolymers; dynamicallyvulcanized elastomers; copolymers of ethylene and vinyl acetates;copolymers of ethylene and methyl acrylates; polyvinyl chloride resins;polyamides, poly(amide-ester) elastomers, and graft copolymers ofionomer and polyamide including, for example, Pebax® thermoplasticpolyether block amides, commercially available from Arkema Inc;cross-linked trans-polyisoprene and blends thereof; polyester-basedthermoplastic elastomers, such as Hytrel®, commercially available fromDuPont or RiteFlex®, commercially available from Ticona EngineeringPolymers; polyurethane-based thermoplastic elastomers, such asElastollan®, commercially available from BASF; synthetic or naturalvulcanized rubber; and combinations thereof. Castable polyurethanes,polyureas, and hybrids of polyurethanes-polyureas are particularlydesirable because these materials can be used to make a golf ball havinghigh resiliency and a soft feel. By the term, “hybrids of polyurethaneand polyurea,” it is meant to include copolymers and blends thereof.

Polyurethanes, polyureas, and blends, copolymers, and hybrids ofpolyurethane/polyurea are also particularly suitable for forming coverlayers. When used as cover layer materials, polyurethanes and polyureascan be thermoset or thermoplastic. Thermoset materials can be formedinto golf ball layers by conventional casting or reaction injectionmolding techniques. Thermoplastic materials can be formed into golf balllayers by conventional compression or injection molding techniques.

The compositions used to make the casing (mantle) and cover layers maycontain a wide variety of fillers and additives to impart specificproperties to the ball. For example, relatively heavy-weight andlight-weight metal fillers such as, particulate; powders; flakes; andfibers of copper, steel, brass, tungsten, titanium, aluminum, magnesium,molybdenum, cobalt, nickel, iron, lead, tin, zinc, barium, bismuth,bronze, silver, gold, and platinum, and alloys and combinations thereofmay be used to adjust the specific gravity of the ball. Other additivesand fillers include, but are not limited to, optical brighteners,coloring agents, fluorescent agents, whitening agents, UV absorbers,light stabilizers, surfactants, processing aids, antioxidants,stabilizers, softening agents, fragrance components, plasticizers,impact modifiers, titanium dioxide, clay, mica, talc, glass flakes,milled glass, and mixtures thereof.

The inner cover layer preferably has a material hardness within a rangehaving a lower limit of 70 or 75 or 80 or 82 Shore C and an upper limitof 85 or 86 or 90 or 92 Shore C. The thickness of the intermediate layeris preferably within a range having a lower limit of 0.010 or 0.015 or0.020 or 0.030 inches and an upper limit of 0.035 or 0.045 or 0.080 or0.120 inches. The outer cover layer preferably has a material hardnessof 85 Shore C or less. The thickness of the outer cover layer ispreferably within a range having a lower limit of 0.010 or 0.015 or0.025 inches and an upper limit of 0.035 or 0.040 or 0.055 or 0.080inches. Methods for measuring hardness of the layers in the golf ballare described in further detail below.

A single cover or, preferably, an inner cover layer is formed around theouter core layer. When an inner cover layer is present, an outer coverlayer is formed over the inner cover layer. Most preferably, the innercover is formed from an ionomeric material and the outer cover layer isformed from a polyurethane material, and the outer cover layer has ahardness that is less than that of the inner cover layer. Preferably,the inner cover has a hardness of greater than about 60 Shore D and theouter cover layer has a hardness of less than about 60 Shore D. In analternative embodiment, the inner cover layer is comprised of apartially or fully neutralized ionomer, a thermoplastic polyesterelastomer such as Hytrel™, commercially available form DuPont, athermoplastic polyether block amide, such as Pebax™, commerciallyavailable from Arkema, Inc., or a thermoplastic or thermosettingpolyurethane or polyurea, and the outer cover layer is comprised of anionomeric material. In this alternative embodiment, the inner coverlayer has a hardness of less than about 60 Shore D and the outer coverlayer has a hardness of greater than about 55 Shore D and the innercover layer hardness is less than the outer cover layer hardness.

As discussed above, the core structure of this invention may be enclosedwith one or more cover layers. In one embodiment, a multi-layered covercomprising inner and outer cover layers is formed, where the inner coverlayer has a thickness of about 0.01 inches to about 0.06 inches, morepreferably about 0.015 inches to about 0.040 inches, and most preferablyabout 0.02 inches to about 0.035 inches. In this version, the innercover layer is formed from a partially- or fully-neutralized ionomerhaving a Shore D hardness of greater than about 55, more preferablygreater than about 60, and most preferably greater than about 65. Theouter cover layer, in this embodiment, preferably has a thickness ofabout 0.015 inches to about 0.055 inches, more preferably about 0.02inches to about 0.04 inches, and most preferably about 0.025 inches toabout 0.035 inches, with a hardness of about Shore D 80 or less, morepreferably 70 or less, and most preferably about 60 or less. The innercover layer is harder than the outer cover layer in this version. Apreferred outer cover layer is a castable or reaction injection moldedpolyurethane, polyurea or copolymer, blend, or hybrid thereof having aShore D hardness of about 40 to about 50. In another multi-layer cover,dual-core embodiment, the outer cover and inner cover layer materialsand thickness are the same but, the hardness range is reversed, that is,the outer cover layer is harder than the inner cover layer. For thisharder outer cover/softer inner cover embodiment, the ionomer resinsdescribed above would preferably be used as outer cover material.

Manufacturing of Golf Balls

As described above, the inner core preferably is formed by a castingmethod. The outer core layer, which surrounds the inner core, is formedby molding compositions over the inner core. Compression or injectionmolding techniques may be used to form the other layers of the coresub-assembly. Then, the casing and/or cover layers are applied over thecore sub-assembly. Prior to this step, the core structure may besurface-treated to increase the adhesion between its outer surface andthe next layer that will be applied over the core. Suchsurface-treatment may include mechanically or chemically-abrading theouter surface of the core. For example, the core may be subjected tocorona-discharge, plasma-treatment, silane-dipping, or other treatmentmethods known to those in the art.

The cover layers are formed over the core or ball sub-assembly (the corestructure and any casing layers disposed about the core) using asuitable technique such as, for example, compression-molding,flip-molding, injection-molding, retractable pin injection-molding,reaction injection-molding (RIM), liquid injection-molding, casting,spraying, powder-coating, vacuum-forming, flow-coating, dipping,spin-coating, and the like. Preferably, each cover layer is separatelyformed over the ball subassembly. For example, an ethylene acidcopolymer ionomer composition may be injection-molded to producehalf-shells. Alternatively, the ionomer composition can be placed into acompression mold and molded under sufficient pressure, temperature, andtime to produce the hemispherical shells. The smooth-surfacedhemispherical shells are then placed around the core sub-assembly in acompression mold. Under sufficient heating and pressure, the shells fusetogether to form an inner cover layer that surrounds the sub-assembly.In another method, the ionomer composition is injection-molded directlyonto the core sub-assembly using retractable pin injection molding. Anouter cover layer comprising a polyurethane or polyurea composition overthe ball sub-assembly may be formed by using a casting process.

After the golf balls have been removed from the mold, they may besubjected to finishing steps such as flash-trimming, surface-treatment,marking, coating, and the like using techniques known in the art. Forexample, in traditional white-colored golf balls, the white-pigmentedcover may be surface-treated using a suitable method such as, forexample, corona, plasma, or ultraviolet (UV) light-treatment. Then,indicia such as trademarks, symbols, logos, letters, and the like may beprinted on the ball's cover using pad-printing, ink-jet printing,dye-sublimation, or other suitable printing methods. Clear surfacecoatings (for example, primer and top-coats), which may contain afluorescent whitening agent, are applied to the cover. The resultinggolf ball has a glossy and durable surface finish.

In another finishing process, the golf balls are painted with one ormore paint coatings. For example, white primer paint may be appliedfirst to the surface of the ball and then a white top-coat of paint maybe applied over the primer. Of course, the golf ball may be painted withother colors, for example, red, blue, orange, and yellow. As notedabove, markings such as trademarks and logos may be applied to thepainted cover of the golf ball. Finally, a clear surface coating may beapplied to the cover to provide a shiny appearance and protect any logosand other markings printed on the ball.

Different ball constructions can be made using the core construction ofthis invention as shown in FIGS. 3-6. Such golf ball constructionsinclude, for example, five-piece, and six-piece constructions. It shouldbe understood that the golf balls shown in FIGS. 3-6 are forillustrative purposes only, and they are not meant to be restrictive.Other golf ball constructions can be made in accordance with thisinvention.

Cores Having Three Layers

For example, multi-layered cores having an inner core, intermediate corelayer, and outer core layer, wherein the intermediate core layer isdisposed between the intermediate and outer core layers may be preparedin accordance with this invention. More particularly, as discussedabove, the inner core may be constructed from a foamed composition,preferably foamed polyurethane. Meanwhile, the intermediate and outercore layers may be formed from non-foamed thermoset or thermoplasticmaterials. Suitable thermoset and thermoplastic compositions that may beused to form the intermediate/outer core layers are discussed above. Forexample, each of the intermediate and outer core layers may be formedfrom a thermoset rubber composition. Thus, the intermediate core layermay be formed from a first thermoset rubber composition; and the outercore layer may be formed from a second thermoset rubber composition. Inanother embodiment, the intermediate core layer is formed from anon-foamed thermoset composition; and the outer core layer is formedfrom a non-foamed thermoplastic composition. In a third embodiment, theintermediate core layer is formed from a non-foamed thermoplasticcomposition; and the outer core layer is formed from a non-foamedthermoset composition. Finally, in a fourth embodiment, the intermediatecore layer is formed from a first non-foamed thermoplastic composition;and the outer core layer is formed from a second non-foamedthermoplastic compositions.

The above-discussed thermoset and thermoplastic compositions may be usedto form the intermediate and outer core layers. In one embodiment, thespecific gravity of the inner core (foamed composition) is less than thespecific gravity of the intermediate and outer core layers. The specificgravities of the intermediate and outer core layers may be the same ordifferent. In one version, the specific gravity of the intermediate corelayer is greater than the specific gravity of the outer core layer. Inanother version, the specific gravity of the outer core is greater thanthe specific gravity of the intermediate core layer.

Cores Having Two or More Foam Layers

In another example, cores having two or more layers comprising foamedcompositions may be made in accordance with this invention. In oneembodiment, a dual-core structure having an inner core layer comprisinga first foamed silicone composition, and an outer core layer comprisinga second foamed silicone composition is made. The inner core layerpreferably has a diameter in the range of about 0.100 to about 1.100inches and the outer core layer preferably has a thickness in the rangeof about 0.100 to about 0.750 inches. The specific gravity of the outercore (SG_(outer)) is preferably greater than the specific gravity of theinner core (SG_(inner)). Alternatively, the inner core may have agreater specific gravity than the outer core's specific gravity. In yetanother version, the specific gravities of the inner and outer corelayers are substantially equivalent. Furthermore, the inner cover layer,which surrounds the core sub-assembly, may be foamed or non-foamed.Suitable thermoset and thermoplastic compositions that may be used toform the foam compositions for constructing the different core and coverlayers are discussed above. For example, in another embodiment, adual-core structure having an inner core layer comprising a first foamedsilicone composition, and an outer core layer comprising a foamedpolyurethane composition is made. Thus, the silicone foam composition ofthis invention is preferably used to manufacture the inner core layer(center), but it also may be used to make intermediate and outer corelayers in accordance with this invention. It also is recognized that thesilicone foam composition may be used to manufacture non-core layers inthe golf ball including, but not limited to, the intermediate (casing)layers and inner and outer cover layers.

Where more than one foam layer is used in a single golf ball, therespective foamed chemical compositions may be the same or different,and the compositions may have the same or different hardness or specificgravity levels. For example, a golf ball may contain a dual-core havinga foamed silicone center with a specific gravity of about 0.40 g/cc anda geometric center hardness of about 50 Shore C and a center surfacehardness of about 75 Shore C. Meanwhile, the outer core layer may bemade from a foamed highly-neutralized ionomer (HNP) composition, whereinthe outer core layer has a specific gravity of about 0.80 g/cc and asurface hardness of about 80 Shore C.

In another example, a golf ball having a foamed center made of a foamedsilicone composition and a surrounding outer core layer made of a foamedhighly-neutralized ionomer (HNP) may be made. In one embodiment, thefoamed center has a specific gravity of about 0.40 g/cc, and the foamedouter core layer has a specific gravity of about 0.80 g/cc. In a thirdexample, a silicone foam center (0.50 inch diameter) is encased in a HNPfoam outer core layer (0.06 inch thickness). The inner foamed siliconecore has a specific gravity of 0.5 g/cc and a surface hardness of 80Shore C, while the outer foamed HNP core has a specific gravity of 0.90g/cc and a surface hardness of 70 Shore C. The dual-core is enclosed ina dual-cover, wherein the inner cover is made of a relatively hardionomer composition (for example, a 50/50 blend of Surlyn® 7940 andSurlyn® 8940 or a 50/50 blend of Surlyn® 9910/Surlyn® 8940) preferablyhaving a thickness of 0.06 inches and an outer cover made of arelatively soft polyurethane composition preferably having a thicknessof 0.03 inches.

In a fourth example, a rigid foam outer core layer comprising athermoset polyurethane foam composition is molded over an inner core(center) comprising a HNP foam composition to provide a “hard over soft”dual-core that reduces ball spin and increases ball distance. In thisexample, the HNP foam center has a diameter of about 0.50 to about 0.80inches, and the outer core layer of cast, thermoset foam has an outerdiameter of about 1.30 to about 1.58 inches. The dual-core is enclosedin a dual-cover, wherein the inner cover is made of a relatively hardionomer composition (for example, a 50/50 blend of Surlyn® 7940 andSurlyn® 8940 or a 50/50 blend of Surlyn® 9910/Surlyn® 8940) preferablyhaving a thickness of 0.06 inches and an outer cover made of arelatively soft polyurethane composition preferably having a thicknessof 0.03 inches. In this embodiment, either the inner cover comprisingthe ionomer blend or the outer cover comprising the polyurethanepreferably contains a sufficient amount of heavy filler to adjust theweight of the golf ball so that it is at least 44 grams, preferably 45.0to 45.9 grams. In an alternative embodiment, a relatively softpolyurethane foam composition is used to form the inner core (center) asopposed to the foamed HNP composition. The soft polyurethane foammaterial used to form the inner core preferably has a different chemicalcomposition than the soft polyurethane material used to form the outercover.

Furthermore, multi-layered cores having an inner core, intermediate corelayer, and outer core layer (as discussed above) may be made, wherein atleast two of the layers comprise foamed compositions. The core may haveadjoining foam layers, for example, the inner core and intermediate corelayers may be made of foamed silicone compositions, while the outer corelayer may be made of a non-foamed thermoset or thermoplasticcomposition. For example, a polybutadiene foamed center (0.50 inchdiameter) is encased in a partially-neutralized ionomer foamedintermediate core layer (0.050 inch thickness). The inner foamedpolybutadiene core may have a specific gravity of 0.85 g/cc and asurface hardness of 65 Shore C, while the partially-neutralized ionomerfoamed intermediate core layer may have a specific gravity of 0.70 g/ccand a surface hardness of 85 Shore C. An outer core layer made of arelative hard HNP ionomer composition having a specific gravity of 0.70g/cc and a surface hardness of 85 Shore C surrounds the intermediatecore layer. The three-layered core structure (“triple core”) is enclosedin a dual-cover, wherein the inner cover is made of a relatively hardionomer composition and an outer cover made of a relatively softpolyurethane composition.

In an alternative version, the core may have a non-foamed thermoset orthermoplastic layer disposed between two foam layers. For example, theinner and outer core layers may be made of a foamed siliconecomposition, and these layers may form a sandwich around an intermediatecore layer made of a non-foamed thermoset or thermoplastic compositionsuch as polybutadiene rubber.

Test Methods

Hardness.

The center hardness of a core is obtained according to the followingprocedure. The core is gently pressed into a hemispherical holder havingan internal diameter approximately slightly smaller than the diameter ofthe core, such that the core is held in place in the hemisphericalportion of the holder while concurrently leaving the geometric centralplane of the core exposed. The core is secured in the holder byfriction, such that it will not move during the cutting and grindingsteps, but the friction is not so excessive that distortion of thenatural shape of the core would result. The core is secured such thatthe parting line of the core is roughly parallel to the top of theholder. The diameter of the core is measured 90 degrees to thisorientation prior to securing. A measurement is also made from thebottom of the holder to the top of the core to provide a reference pointfor future calculations. A rough cut is made slightly above the exposedgeometric center of the core using a band saw or other appropriatecutting tool, making sure that the core does not move in the holderduring this step. The remainder of the core, still in the holder, issecured to the base plate of a surface grinding machine. The exposed‘rough’ surface is ground to a smooth, flat surface, revealing thegeometric center of the core, which can be verified by measuring theheight from the bottom of the holder to the exposed surface of the core,making sure that exactly half of the original height of the core, asmeasured above, has been removed to within 0.004 inches. Leaving thecore in the holder, the center of the core is found with a center squareand carefully marked and the hardness is measured at the center markaccording to ASTM D-2240. Additional hardness measurements at anydistance from the center of the core can then be made by drawing a lineradially outward from the center mark, and measuring the hardness at anygiven distance along the line, typically in 2 mm increments from thecenter. The hardness at a particular distance from the center should bemeasured along at least two, preferably four, radial arms located 180°apart, or 90° apart, respectively, and then averaged. All hardnessmeasurements performed on a plane passing through the geometric centerare performed while the core is still in the holder and without havingdisturbed its orientation, such that the test surface is constantlyparallel to the bottom of the holder, and thus also parallel to theproperly aligned foot of the durometer.

The outer surface hardness of a golf ball layer is measured on theactual outer surface of the layer and is obtained from the average of anumber of measurements taken from opposing hemispheres, taking care toavoid making measurements on the parting line of the core or on surfacedefects, such as holes or protrusions. Hardness measurements are madepursuant to ASTM D-2240 “Indentation Hardness of Rubber and Plastic byMeans of a Durometer.” Because of the curved surface, care must be takento ensure that the golf ball or golf ball sub-assembly is centered underthe durometer indenter before a surface hardness reading is obtained. Acalibrated, digital durometer, capable of reading to 0.1 hardness unitsis used for the hardness measurements. The digital durometer must beattached to, and its foot made parallel to, the base of an automaticstand. The weight on the durometer and attack rate conforms to ASTMD-2240.

In certain embodiments, a point or plurality of points measured alongthe “positive” or “negative” gradients may be above or below a line fitthrough the gradient and its outermost and innermost hardness values. Inan alternative preferred embodiment, the hardest point along aparticular steep “positive” or “negative” gradient may be higher thanthe value at the innermost portion of the inner core (the geometriccenter) or outer core layer (the inner surface)—as long as the outermostpoint (i.e., the outer surface of the inner core) is greater than (for“positive”) or lower than (for “negative”) the innermost point (i.e.,the geometric center of the inner core or the inner surface of the outercore layer), such that the “positive” and “negative” gradients remainintact.

As discussed above, the direction of the hardness gradient of a golfball layer is defined by the difference in hardness measurements takenat the outer and inner surfaces of a particular layer. The centerhardness of an inner core and hardness of the outer surface of an innercore in a single-core ball or outer core layer are readily determinedaccording to the test procedures provided above. The outer surface ofthe inner core layer (or other optional intermediate core layers) in adual-core ball are also readily determined according to the proceduresgiven herein for measuring the outer surface hardness of a golf balllayer, if the measurement is made prior to surrounding the layer with anadditional core layer. Once an additional core layer surrounds a layerof interest, the hardness of the inner and outer surfaces of any inneror intermediate layers can be difficult to determine. Therefore, forpurposes of the present invention, when the hardness of the inner orouter surface of a core layer is needed after the inner layer has beensurrounded with another core layer, the test procedure described abovefor measuring a point located 1 mm from an interface is used.

Also, it should be understood that there is a fundamental differencebetween “material hardness” and “hardness as measured directly on a golfball.” For purposes of the present invention, material hardness ismeasured according to ASTM D2240 and generally involves measuring thehardness of a flat “slab” or “button” formed of the material. Surfacehardness as measured directly on a golf ball (or other sphericalsurface) typically results in a different hardness value. The differencein “surface hardness” and “material hardness” values is due to severalfactors including, but not limited to, ball construction (that is, coretype, number of cores and/or cover layers, and the like); ball (orsphere) diameter; and the material composition of adjacent layers. Italso should be understood that the two measurement techniques are notlinearly related and, therefore, one hardness value cannot easily becorrelated to the other. Shore hardness (for example, Shore C or Shore Dor Shore A hardness) was measured according to the test method ASTMD-2240.

Compression.

As disclosed in Jeff Dalton's Compression by Any Other Name, Science andGolf IV, Proceedings of the World Scientific Congress of Golf (EricThain ed., Routledge, 2002) (“J. Dalton”), several different methods canbe used to measure compression, including Atti compression, Riehlecompression, load/deflection measurements at a variety of fixed loadsand offsets, and effective modulus. For purposes of the presentinvention, compression refers to Soft Center Deflection Index (“SCDI”).The SCDI is a program change for the Dynamic Compression Machine (“DCM”)that allows determination of the pounds required to deflect a core 10%of its diameter. The DCM is an apparatus that applies a load to a coreor ball and measures the number of inches the core or ball is deflectedat measured loads. A crude load/deflection curve is generated that isfit to the Atti compression scale that results in a number beinggenerated that represents an Atti compression. The DCM does this via aload cell attached to the bottom of a hydraulic cylinder that istriggered pneumatically at a fixed rate (typically about 1.0 ft/s)towards a stationary core. Attached to the cylinder is an LVDT thatmeasures the distance the cylinder travels during the testing timeframe.A software-based logarithmic algorithm ensures that measurements are nottaken until at least five successive increases in load are detectedduring the initial phase of the test. The SCDI is a slight variation ofthis set up. The hardware is the same, but the software and output haschanged. With the SCDI, the interest is in the pounds of force requiredto deflect a core x amount of inches. That amount of deflection is 10%percent of the core diameter. The DCM is triggered, the cylinderdeflects the core by 10% of its diameter, and the DCM reports back thepounds of force required (as measured from the attached load cell) todeflect the core by that amount. The value displayed is a single numberin units of pounds.

Coefficient of Restitution (“COR”).

The COR is determined according to a known procedure, wherein a golfball or golf ball sub-assembly (for example, a golf ball core) is firedfrom an air cannon at two given velocities and a velocity of 125 ft/s isused for the calculations. Ballistic light screens are located betweenthe air cannon and steel plate at a fixed distance to measure ballvelocity. As the ball travels toward the steel plate, it activates eachlight screen and the ball's time period at each light screen ismeasured. This provides an incoming transit time period which isinversely proportional to the ball's incoming velocity. The ball makesimpact with the steel plate and rebounds so it passes again through thelight screens. As the rebounding ball activates each light screen, theball's time period at each screen is measured. This provides an outgoingtransit time period which is inversely proportional to the ball'soutgoing velocity. The COR is then calculated as the ratio of the ball'soutgoing transit time period to the ball's incoming transit time period(COR=V_(out)/V_(in)=T_(in)/T_(out)).

Density.

The density refers to the weight per unit volume (typically, g/cm³) ofthe material and can be measured per ASTM D-1622.

It is understood that the golf ball compositions, constructions, andproducts described and illustrated herein represent only someembodiments of the invention. It is appreciated by those skilled in theart that various changes and additions can be made to compositions,constructions, and products without departing from the spirit and scopeof this invention. It is intended that all such embodiments be coveredby the appended claims.

We claim:
 1. A golf ball, comprising: i) a core having at least onelayer; ii) an inner cover layer comprising a silicone elastomercomposition, wherein the silicone elastomer composition is made from atleast one heterobifunctional macromer and the composition has anelongation greater than 2000%, the inner cover layer being disposedabout the core and having a midpoint hardness in the range of about 55to about 75 Shore A; and iii) an outer cover layer disposed about theinner cover layer and having an outer surface hardness in the range ofabout 20 to about 60 Shore D.
 2. The golf ball of claim 1, wherein theinner cover layer has a thickness in the range of about 0.010 to about0.075 inches.
 3. The golf ball of claim 1, wherein the siliconeelastomer composition has an elongation greater than 3000%.
 4. The golfball of claim 1, wherein the outer cover layer comprises a polymerselected from the group consisting of: ethylene acid copolymer ionomers;polyesters; polyamides; polyurethanes, polyureas; fluoropolymers;polystyrenes; polypropylenes, polyethylenes; polyvinyl chlorides;polyvinyl acetates; polycarbonates; polyvinyl alcohols; polyethers;polyimides, polyetherketones, polyamideimides; and mixtures thereof. 5.The golf ball of claim 4, wherein the outer cover comprises an ethyleneacid copolymer containing acid groups such that less than 70% of theacid groups are neutralized.
 6. The golf ball of claim 4, wherein theouter cover comprises an ethylene acid copolymer containing acid groupssuch that greater than 70% of the acid groups are neutralized.
 7. Thegolf ball of claim 1, wherein the outer cover comprises a polymerselected from the group consisting of polyurethanes, polyueas,polyurethane-urea hybrids, and copolymers and blends thereof.
 8. A golfball, comprising: i) an inner core layer comprising a thermoset rubbercomposition, the inner core layer having a diameter in the range ofabout 0.100 to about 1.100 inches, and an outer surface hardness(H_(inner core surface)) and a center hardness (H_(inner core center)),the H_(inner core surface) being greater than the H_(inner core center)to provide a positive hardness gradient; ii) an intermediate core layercomprising a silicone elastomer composition, wherein the siliconeelastomer composition is made from at least one heterobifunctionalmacromer and the composition has an elongation greater than 2000%, theintermediate layer being disposed about the inner core and having athickness in the range of about 0.050 to about 0.400 inches, and anouter surface hardness (H_(outer surface of IC)) and a midpoint hardness(H_(midpoint of IC)), the H_(outer surface of IC) being the same or lessthan the H_(midpoint of IC) to provide a zero or negative hardnessgradient; and iii) an outer core layer comprising a thermoset rubbercomposition, the outer core layer being disposed about the intermediatecore layer and having a thickness in the range of about 0.200 to about0.750 inches, and an outer surface hardness (H_(outer surface of OC))and an inner surface hardness (H_(inner surface of OC)), theH_(outer surface of OC) being greater than the H_(inner surface of OC)to provide to positive hardness gradient; and, iv) a cover having atleast one layer.
 9. The golf ball of claim 8, wherein the inner core andouter core layer comprises at least one thermoset rubber materialselected from the group consisting of polybutadiene, ethylene-propylenerubber, ethylene-propylene-diene rubber, polyisoprene, styrene-butadienerubber, polyalkenamers, butyl rubber, halobutyl rubber, polystyreneelastomers, copolymers of isobutylene and p-alkylstyrene, halogenatedcopolymers of isobutylene and p-alkylstyrene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber, and mixturesthereof.
 10. The golf ball of claim 8, wherein the H_(inner core center)is in the range of about 10 Shore C to about 70 Shore C and theH_(outer surface of OC) is in the range of about 20 Shore C to about 95Shore C to provide a positive hardness gradient across the coreassembly.
 11. The golf ball of claim 8, wherein the H_(midpoint of IC)is in the range of about 27 Shore A to about 80 Shore A, and theH_(outer surface of IC) is in the range of about 23 Shore A to and about73 Shore A to provide a zero or negative hardness gradient.